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Supporting Information for
Selective Incorporation of Primary Amines into a Tri-zirconium
Imido System and Catalytic Cyclization of Aminoalkynes
Masataka Oishi,‡* Yusuke Nakanishi,† and Hiroharu Suzuki† ‡School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 O-okayama,
Meguro-ku, Tokyo 152-8552, Japan †Graduate School of Science and Engineering, Tokyo Institute
of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan
INDEX
General procedures ··············································································································· S2
Instrumentation ··············································································································· S2
Figure S1 ·································································································································· S3
Synthesis of 2 ··············································································································· S4
NMR-scale reaction of 2 with n-PrNH2 ·········································································· S4
Figures S2-1 and S2-2 ··············································································································· S6
NMR-scale reaction of 2 with EtNH2 ·········································································· S7
NMR-scale reaction of 2 with i-BuNH2 ·········································································· S8
Reaction of 2 with neo-PenNH2 ····························································································· S8
Reaction of 2 with anilines ····························································································· S9
Figure S3 ·································································································································· S11
Synthesis of 7 ··············································································································· S12
Reaction of 8 with neo-PenNH2 ····························································································· S12
Figure S4 ·································································································································· S13
Figures S5 and S6 ··············································································································· S14
Figure S7 ·································································································································· S15
Figure S8 ·································································································································· S16
Thermolysis of 3 and 4 ··············································································································· S17
Figures S9 and S10 ··············································································································· S18
Synthesis of 13c and 14a ····························································································· S19
Catalytic cyclization of aminoalkynes 13 and 14 ······················································· S21
Figure S11 ·································································································································· S22
Stoichiometric reaction of 2 and 13c ·········································································· S22
Figure S12 ·································································································································· S23
Figure S13 ·································································································································· S24
Semi-catalytic reaction of 2 and 14b ·········································································· S25
Figure S14 ·································································································································· S25
Figure S15 ·································································································································· S26
Figure S16 ·································································································································· S27
Table S1 ································································································································ S28
NMR spectra ·············································································································· S31
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General Procedures. All manipulations for air- and moisture-sensitive compounds were carried out
under an argon atmosphere using standard Schlenk techniques or in a glovebox filled with argon or
nitrogen (H2O < 1 ppm, O2 < 1 ppm). Dehydrated solvents (tetrahydrofuran, toluene, pentane, ether)
were purchased from Kanto Chemical Co. Ltd. Deuterated solvents (benzene-d6, chloroform-d,
toluene-d8) were purchased from Cambridge Isotope Laboratories, Inc and Sigma-Aldrich Co.
Deuterated/non-deuterated hydrocarbon and ethereal solvents were distilled from Na-K alloy and
stored under an argon atmosphere. Commercially available organic substrates were purified by
distillation or sublimation. Other reagents and organic chemicals were used as received.
2-(2,3,4,5-Tetramethylcyclopentadienyl)ethanamine,1 Me2Si(η5-C5Me4)(Nt-Bu)Zr(NMe2)2 (8),2 and
aminoalkynes 13a, 13b, and 14b3 were prepared according to the literature procedures or the
modified ones.
Instrumentation. 1H and 13C NMR spectra were recorded on Varian INOVA 400 and Varian
400-MR Fourier transform spectrometers. 1H chemical shifts were referenced to the residual proton
peaks of benzene-d6 at δ 7.15 ppm, chloroform-d at δ 7.25 ppm, or toluene-d8 (meta-proton) at δ 7.09
ppm vs. tetramethylsilane. NMR yields were estimated by integration changes based on integrations
of bis(trimethylsilyl)methane as an internal standard. The central peaks of triplet for benzene-d6 at δ
128.1 ppm or chloroform-d at δ 77.2 ppm vs. tetramethylsilane were used as 13C NMR internal
references. Elemental analyses were recorded on a Perkin-Elmer 2400II. Single crystals suitable for
X-ray analysis were coated with Paratone-N in a glovebox. Crystals of proper size were picked by
using nylon CryoLoopTM and quickly transferred in a low temperature N2 stream to the goniometer
head. The diffraction data were collected on a R-AXIS RAPID diffractometer equipped with
graphite-monochromated Mo Kα radiation (λ = 0.71069 Å). Structures were solved by using
SHELXT and expanded using Fourier techniques. The non-hydrogen atoms were refined by
full-matrix least-square refinement in F2 using SHELXL 2014.4 Hydrogen atoms were located by
difference Fourier maps and refined isotropically. Crystal, measurement, refinement data for
complexes 2, 3a, 4a, 4c, 5, 6b, and 7 are summarized in Table S1.
1 Van Leusen, D.; Beetstra, D. J.; Hessen, B.; Teuben, J. H. Organometallics 2000, 19, 4084. 2 Carpenetti, D. W.; Kloppenburg, L.; Kupec, J. T.; Petersen, J. L. Organometallics 1996, 15, 1572. 3 (a) Li, Y.; Fu, P.-F.; Marks, T. J. Organometallics 1994, 13, 439. (b) McGrane, P. L.; Jensen, M.; Livinghouse, T. J. Am. Chem. Soc. 1992, 114, 5459. (c) Duncan, D.; Livinghouse, T. Organometallics 1999, 18, 4421. 4 G. M. Sheldrick, SHELXTL Version 2014/7. http://shelx.uni-ac.gwdg.de/SHELX/index.php.
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Figure S1. 1H NMR spectra of exo-olefinic isomer-major sample of 1 (top) and an isomeric mixture
of 1 after isomerization by HCl (bottom) (solvent: CDCl3). The asterisks denote solvent signals.
major*
*
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Synthesis of 2
(2,3,4,5-Tetramethylcyclopenta-1,4-dienyl)-1-ethanamine (1) (4.20 mmol, 0.70 g) was dissolved in
dry toluene (40 mL) under argon atmosphere. In a glovebox, Zr(NMe2)4 (4.20 mmol, 1.15 g) was
added to the solution at ambient temperature. After evacuated at –78 ºC, the mixture was heated at
60 ºC for 40 h. Then, all volativels were removed under reduced pressure and the residue was
washed with pentane and dried in vacuo to afford 2 as a light yellow powder (0.67 g, 54%). Crystals
suitable for X-ray analysis was obtained from toluene at –30 ºC. Note that the corresponding
reaction with the exo-olefin isomer of 1 [i.e., 2-(2,3,4,5-tetramethyl-2-cyclopenten-1-
ylidene)ethanamine] does not produce complex 2. The following NMR assignments for 2 were made
by COSY, HMQC, and HMBC experiments.
[(LZrNMe2)3] (2) (L = η5-C5Me4CH2CH2N): 1H NMR (C6D6, 400 MHz): δ 4.71 (1H, ddd, J = 6.4,
10.8, 13.5 Hz, NCHHCH2), 4.60 (1H, ddd, J = 6.4, 10.5, 13.4 Hz, N′CHHCH2), 4.22 (1H, ddd, J =
5.8, 10.1, 12.4 Hz, N″CHHCH2), 3.92 (1H, ddd, J = 2.3, 5.6, 12.4 Hz, N″CHHCH2), 3.60 (1H, dd, J
= 5.8, 13.5 Hz, NCHHCH2), 3.47 (1H, dd, J = 5.8, 13.4 Hz, N′CHHCH2), 2.97 (6H, s, NMe2), 2.95
(6H, s, NMe2), 2.76 (6H, s, NMe2), 2.77–2.70 (1H, overlap, NCH2CHH), 2.76–2.67 (1H, overlap,
N′CH2CHH), 2.74–2.67 (1H, overlap, NCH2CHH), 2.72–2.65 (1H, overlap, N′CH2CHH), 2.67–2.60
(1H, overlap, N″CH2CHH), 2.65–2.59 (1H, overlap, N″CH2CHH), 2.12, 2.100, 2.096, 2.05, 2.05,
2.01, 1.98, 1.98, 1.96, 1.94, 1.92, 1.91 (3H × 12, s, C5Me4 × 3) ppm. 13C{1H} NMR (C6D6, 100
MHz): δ 130.3, 130.0, 125.9, 120.9, 119.6, 118.7, 118.6, 118.3, 117.8, 116.6, 116.0, 115.0, 114.2,
113.7, 113.5 (C5Me4 × 3), 60.7 (NCH2CH2), 59.7 (N′CH2CH2), 58.5 (N″CH2CH2), 46.7 (NMe2),
46.1 (NMe2), 44.8 (NMe2), 29.5 (N″CH2CH2), 28.7 (NCH2CH2), 28.3 (N′CH2CH2), 12.9, 11.7, 11.60,
11.58, 11.1, 10.9, 10.9, 10.8, 10.73, 10.69, 10.63, 10.55 (C5Me4 × 3) ppm. Anal. Calcd for
C39H66N6Zr3: C, 52.47; H, 7.45; N, 9.41. Found: C, 52.70; H, 7.39; N, 9.50.
NMR-scale reaction of 2 with n-PrNH2
(i) Reaction monitoring at 25 °C
In the glovebox, complex 2 (6.3 μmol, 5.6 mg) was dissolved in C6D6 (0.4 mL) with the internal
standard (Me3Si)2CH2. An NMR spectrum was recorded before addition of n-PrNH2. A solution of
n-PrNH2 (1.1 M in C6D6, 57 μmol, 52 μL) was then added at 25 °C. The reaction was monitored by 1H NMR analysis. About 4 equiv of n-PrNH2 was reacted with 2 in 15 min, producing almost a
single product 3akinetic. However, the product gradually disappeared and, after 16 h, was mostly
replaced by a thermodynamically stable structure 3a with no change of intensity of free n-PrNH2.
The yield of 3a at t = 16 h was estimated by 1H NMR analysis to be 92%. NMR data of 3akinetic and
3a are given below, and the 1H NMR comparison is shown in Figure S2-1 and S2-2.
3akinetic: Partial 1H NMR (C6D6, 400 MHz): δ 4.85–4.73 (2H, m), 4.48 (1H, dd, J = 4.0, 12.0 Hz),
4.03–3.92 (1H, m), 3.65–3.43 (2H, m), 3.41–3.14 (4H, m), 3.12–2.98 (2H, m), 2.91–2.69 (3H, m),
Page 5
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2.65–2.52 (2H, m), 2.52–2.43 (1H, m), 2.34–2.25 (3H, m), 2.23, 2.20, 2.17, 2.17, 2.14, 2.11, 1.997,
1.991, 1.97, 1.92 (3H × 12, s, C5Me4 × 3), 2.00–1.77 (2H, m), 1.63–1.34 (6H, m), 1.06–0.98 (10H, m,
μ-NCH2CH2CH3 × 3 and other), 0.93 (3H, t, J = 7.4 Hz, NHCH2CH2CH3), 0.82–0.71 (1H, m), 0.29
(1H, br d, J = 6.4 Hz) ppm.
[(LZrNHPr)(LHZrNHPr)(LHZr)(μ-NHPr)(μ3-NPr)] (3a): 1H NMR (C6D6, 400 MHz): δ
4.54–4.46 (1H, overlap, NCHHCH2C5Me4), 4.53–4.44 (1H, overlap, HN1CH2CH2CH3), 4.38 (1H,
dd, J = 4.9, 11.8 Hz, HN2CH2CH2CH3), 4.09 (1H, dt-like ddd, J = 2.6, 13.2 Hz, N3CHHCH2CH3),
3.97 (1H, dt-like ddd, J = 2.0, 12.8 Hz, HN′CHHCH2C5Me4), 3.82 (1H, dt-like ddd, J = 5.9, 12.4 Hz,
N3CHHCH2CH3), 3.70 (1H, m, HN2CHHCH2CH3), 3.66–3.53 (1H, overlap, HN″CHHCH2C5Me4),
3.66–3.52 (1H, overlap, NCHHCH2C5Me4), 3.60–3.50 (1H, overlap, HN′CHHCH2C5Me4),
3.56–3.41 (2H, overlap, HN1CH2CH2CH3), 3.45–3.35 (1H, overlap, HN″CHHCH2C5Me4), 3.31 (1H,
m, HN2CHHCH2CH3), 2.84 (2H, m, HN4CH2CH2CH3), 2.63–2.52 (2H, overlap, NCH2CH2C5Me4),
2.50–2.34 (2H, overlap, HN′CH2CH2C5Me4), 2.48–2.36 (1H, overlap, HN″CH2CHHC5Me4),
2.36–2.28 (1H, overlap, HN″CH2CHHC5Me4), 2.27, 2.20, 2.19, 2.18, 2.17, 2.15, 2.14, 2.01, 2.01,
1.95, 1.91, 1.88 (3H × 12, s, C5Me4 × 3), 1.71 (1H, m, HN4CH2CHHCH3), 1.63–1.50 (1H, overlap,
N3CH2CHHCH3), 1.56–1.45 (2H, overlap, HN2CH2CH2CH3), 1.55–1.42 (2H, overlap,
HN1CH2CH2CH3), 1.38 (1H, m, HN4CH2CHHCH3), 1.06 (3H, t, J = 7.4 Hz, HN2CH2CH2CH3), 1.01
(3H, t, J = 7.2 Hz, HN1CH2CH2CH3), 1.01–0.98 (1H, overlap, N3CH2CHHCH3), 0.95 (3H, t, J = 6.7
Hz, N3CH2CH2CH3), 0.93 (3H, t, J = 7.3 Hz, HN4CH2CH2CH3), 0.88–0.74 (1H, overlap,
HN″CH2CH2C5Me4), 0.82–0.72 (1H, overlap, HN′CH2CH2C5Me4), 0.37 (1H, dd, J = 5.1, 9.0 Hz,
HN4CH2CH2CH3) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 129.6, 128.6, 122.3, 122.1, 118.3, 118.0,
117.6, 117.5, 116.6, 116.4, 116.1, 115.2, 115.0, 114.4, 113.8 (C5Me4 × 3), 63.0 (NCH2), 60.1
(HN′CH2), 55.7 (HN″CH2), 59.7 (N3CH2), 55.9 (HN4CH2), 54.7 (HN2CH2), 54.4 (HN1CH2), 31.5,
31.3, 28.9 (NCH2CH2C5Me4 × 3), 30.7 (N3CH2CH2), 30.4 (HN4CH2CH2), 30.0 (HN2CH2CH2), 29.5
(HN1CH2CH2), 13.4, 13.2, 13.1, 12.4, 12.2, 12.1, 11.9, 11.54, 11.47, 11.43, 11.38, 10.6 (C5Me4 × 3),
12.9 (N3CH2CH2CH3), 12.7 (HN4CH2CH2CH3), 12.3 (HN1CH2CH2CH3), 11.6 (HN2CH2CH2CH3)
ppm. Single crystals of 3a were obtained from a concentrated toluene solution at 25 °C and the
structure was determined by XRD analysis.
(ii) Formation of 4a
In the glovebox, 2 (22 μmol, 20 mg) was dissolved in toluene (0.8 mL) in a Teflon-valved Schlenk
tube. Out of the box, n-PrNH2 (97 μmol, 8 μL) was then added under argon purge. After 3 h at 25 °C,
Volatiles were removed under reduced pressure, giving a mixture of 3a and 4a as a waxy oil (20 mg,
combined yield: 95%). The 1H NMR pattern of 4a in the 4a-major sample was compared with that of
3a (containing n-PrNH2) and i-BuNH2-derived 4c. The ratio of 3a and 4a was estimated by integral
values of separated signals of the methyl groups of C5Me4 (δ = 1.91 ppm for 3a and 1.80 ppm for
4a) to be 39:61. Crystals of 4a were eventually obtained from the 4a-major sample and the structure
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of 4a was determined by preliminary XRD analysis and its comparison with that of 4c.
Figure S2-1. 1H NMR spectra of the NMR-scale reaction of 2 and n-PrNH2 (C6D6, 25 °C).
Figure S2-2. Partial 1H NMR spectra of the NMR-scale reaction of 2 and n-PrNH2 (C6D6, 25 °C).
ppm (f1)0.01.02.03.04.05.0
≈≈
≈≈
t = 15 min
t = 16 h
(Me3Si)2CH2 (internal standard)f ree n-PrNH2
ppm (f1)1.701.801.902.002.102.202.30
Me2NH
Me2NH
C5Me4 and NCH2CH2CH3 of 3akineticC5Me4 and NCH2CH2CH3 of 3at= 15 min
t= 16 h
1.00 0.901.10
3H9H
6H3H 3H
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[(LZrNHPr-n)2(LHZr)(μ-NPr-n)] (4a): Partial 1H NMR (C6D6, 400 MHz): δ 4.97 (1H, dd,
NCHHCH2C5Me4), 4.88 (1H, ddd, NCHHCH2C5Me4), 4.49 (2H, m, N′CH2CH2C5Me4), 3.92 (1H,
dt-like ddd, J = 4.2, 11.2 Hz), 3.62 (2H, m), 3.56−3.37 (4H, m, N″CHHCH2C5Me4 + others),
3.37−3.25 (2H, m), 3.05 (1H, td-like ddd, J = 5.6, 13.2 Hz, N″CHHCH2C5Me4), 2.85 (1H, ddd, J =
7.6, 10.8, 12.4 Hz, NCH2CHHC5Me4), 2.78−2.69 (2H, m, NCH2CHHC5Me4 + N′CH2CHHC5Me4),
2.52 (1H, td-like ddd, J = 7.2, 12.8 Hz), 2.39 (2H, m), 2.26, 2.18, 2.18, 2.13, 2.13, 2.12, 2.08, 2.06,
2.03, 1.93, 1.80, 1.71 (3H × 12, s, C5Me4 × 3), 1.59 (2H, m), 1.53–1.38 (2H, m), 1.35 (1H, dd, J =
5.6, 14.0 Hz), 1.09 (3H, t, μ-NCH2CH2CH3), 0.99 (3H × 2, t, NHCH2CH2CH3) ppm.
NMR-scale reaction of 2 with EtNH2
Similarly to the formation of 3a, a NMR-scale reaction of 2 with an excess amount of EtNH2 was
examined. In the box, complex 2 (6.2 μmol, 5.5 mg) and internal standard were dissolved in C6D6
(0.5 mL). After a 1H NMR spectrum was recorded, a THF solution of EtNH2 (2.0 M, 25 μL) was
syringed in at 25 °C. The reaction was monitored by NMR spectroscopy. Singlet signals for C5Me4
groups of 3bkinetic were observed as the major product at t = 20 min. After 21 h, majority of these
signals were replaced by those of 3b: 3bkinetic, 15% NMR yield; 3b, 65% NMR yield. Neither 3bkinetic
nor 3b were isolated and thermodynamically stable 3b was identified by comparison of the
following 1H NMR data with those of 3a.
3bkinetic: Partial 1H NMR (C6D6, 400 MHz): δ 2.17, 2.17, 2.15, 2.14, 2.13, 2.08, 1.99, 1.98, 1.96, 1.94,
1.90, 1.90 (3H × 12, s, C5Me4 × 3) ppm.
[(LZrNHEt)(LHZrNHEt)(LHZr)(μ-NHEt)(μ3-NEt)] (3b): 1H NMR (C6D6, 400 MHz): δ 4.49 (1H,
dd, J = 5.8, 12.6 Hz, NCHHCH2C5Me4), 4.39 (1H, dd, J = 5.4, 11.0 Hz, HN1CH2CH3), 4.33–4.20
(1H, overlap, N3CHHCH3), 4.29 (1H, overlap, HN2CH2CH3), 3.96 (1H, dd, J = 6.2, 13.0 Hz,
HN′CHHCH2C5Me4), 3.90–3.78 (1H, m, N3CHHCH3), 3.80–3.67 (1H, m, HN1CHHCH3), 3.66–3.50
(1H, overlap, HN″CHHCH2C5Me4), 3.65–3.53 (1H, overlap, NCHHCH2C5Me4), 3.60–3.48 (2H,
overlap, HN2CH2CH3), 3.59–3.50 (1H, overlap, HN′CHHCH2C5Me4), 3.46–3.36 (1H, overlap,
HN″CHHCH2C5Me4), 3.44–3.30 (1H, m, HN1CHHCH3), 3.03 (2H, m-like qd, J = 6.9, Hz,
HN4CH2CH3), 2.56 (1H, m, NCH2CHHC5Me4), 2.49–2.38 (1H, overlap, HN″CH2CHHC5Me4),
2.48–2.34 (2H, overlap, HN′CH2CH2C5Me4), 2.42–2.34 (1H, overlap, HN″CH2CHHC5Me4), 2.30
(1H, m, NCH2CHHC5Me4), 2.24, 2.17, 2.160, 2.156, 2.14, 2.13, 2.12, 2.004, 1.996, 1.93, 1.88, 1.87
(3H × 12, s, C5Me4 × 3), 1.20 (3H, t, J = 7.2 Hz, HN4CH2CH3), 1.16 (3H, t, J = 7.0 Hz,
HN1CH2CH3), 1.15 (3H, t, J = 7.0 Hz, HN2CH2CH3), 1.13 (3H, t, J = 7.0 Hz, N3CH2CH3), 0.89–0.78
(1H, overlap, HN″CH2CH2C5Me4), 0.84–0.74 (1H, overlap, HN′CH2CH2C5Me4), 0.22 (1H, t, J = 6.7
Hz, HN4CH2CH3) ppm.
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NMR-scale reaction of 2 with i-BuNH2
In the glovebox, 2 (11 μmol, 10.0 mg) was dissolved in C6D6 (0.4 mL) with the internal standard in a
Teflon-valved NMR tube. i-BuNH2 (55 μmol, 5.5 μL) was added after a 1H NMR spectrum was
recorded. The reaction progress was monitored by NMR spectroscopy. After 12 h, complex 4c was
yielded quantitatively. The structure was determined by NMR and X-ray analysis.
[(LZrNHBu-i)2(LHZr)(μ-NBu-i)] (4c): 1H NMR (C6D6, 400 MHz): δ 4.98 (1H, dd, J = 6.8, 11.4
Hz, NCHHCH2), 4.86 (1H, dt-like ddd, J = 6.8, 11.4 Hz, NCHHCH2), 4.60–4.48 (2H, m,
N′CH2CH2), 3.74 (1H, dd, J = 5.8, 13.0 Hz, N3CHHCHMe2), 3.67 (1H, t-like dd, J = 7.4 Hz,
HN1CH2CHMe2), 3.50 (1H, t-like dd, J = 7.6 Hz, HN2CH2CHMe2), 3.45–3.22 (1H, overlap,
HN1CHHCHMe2), 3.40 (1H, dt-like ddd, J = 4.8, 13.2 Hz, HN″CHHCH2), 3.35–3.25 (1H, overlap,
N3CHHCHMe2), 3.38–3.19 (2H, overlap, HN2CH2CHMe2), 3.13 (1H, td-like ddd, J = 7.4, 12.4 Hz,
HN1CHHCHMe2), 3.03 (1H, td-like ddd, J = 6.0, 13.2 Hz, HN″CHHCH2), 2.85 (1H, m, NCH2CHH),
2.77–2.67 (1H, overlap, N′CH2CHH), 2.75–2.66 (1H, overlap, NCH2CHH), 2.51 (1H, dt-like ddd, J
= 5.6, 12.8 Hz, N′CH2CHH), 2.38 (1H, J = 4.4, 14.0 Hz, HN″CH2CHH), 2.28–2.12 (1H, overlap,
HN″CH2CHH), 2.27, 2.20, 2.18, 2.17, 2.143, 2.12, 2.07, 2.06, 2.03, 1.93, 1.82, 1.69 (3H × 12, s,
C5Me4 × 3), 1.81–1.68 (1H, overlap, N3CH2CHMe2), 1.73–1.60 (1H, overlap, HN2CH2CHMe2), 1.52
(1H, m, HN1CH2CHMe2), 1.40 (1H, dd, J = 6.0, 13.2 Hz, HN″CH2CH2), 1.099 (3H, d, J = 6.4 Hz,
HN2CH2CHMeMe), 1.096 (3H, d, J = 6.8 Hz, HN2CH2CHMeMe), 1.02 (3H, d, J = 6.4 Hz,
HN1CH2CHMeMe), 1.01 (3H, d, J = 6.4 Hz, HN1CH2CHMeMe), 0.95 (3H, d, J = 6.4 Hz,
N3CH2CHMeMe), 0.91 (3H, d, J = 6.4 Hz, N3CH2CHMeMe) ppm. 13C{1H} NMR (C6D6, 100 MHz):
δ 133.7, 125.2, 124.2, 119.5, 119.4, 117.9, 117.0, 116.42, 116.37, 115.6, 115.0, 114.9, 114.7, 114.0,
112.8 (C5Me4 × 3), 72.0 (NCH2CH2), 66.5 (N3CH2CHMe2), 65.7 (N′CH2CH2), 60.6
(HN1CH2CHMe2), 59.3 (HN2CH2CHMe2), 55.9 (HN″CH2CH2), 34.3 (HN1CH2CHMe2), 34.1
(N3CH2CHMe2), 33.8 (HN2CH2CHMe2), 32.1 (N′CH2CH2), 29.3 (NCH2CH2), 29.1 (HN″CH2CH2),
21.5, 21.1, 21.1, 21.0. 21.0, 20.8 (NCH2CHMe2 × 3), 12.1, 12.0, 11.8, 11.76, 11.74, 11.68, 11.6, 11.5,
11.2, 10.93, 10.88, 10.5 (C5Me4 × 3) ppm.
Reaction of 2 with neo-PenNH2
In the glovebox, 2 (0.054 mmol, 48 mg) was dissolved in toluene (8.0 mL). Outside of the box,
neo-PenNH2 (0.33 mmol, 39 μL) was then added to the solution under an argon purge. The mixture
was stirred at ambient temperature for 10 min. Removal of all volatiles gave crude 5, which was
washed with pentane and dried in vacuo, affording a light yellow powder (47 mg, quant).
[(LZr)2(LZrNMe2)(μ-NPen-neo)] (5): 1H NMR (C6D6, 400 MHz): δ 5.15–5.02 (1H, overlap,
NCHHCH2), 5.14–5.03 (1H, overlap, N′CHHCH2), 4.94 (1H, dd, J = 6.6, 12.6, NCHHCH2), 4.80
(2H, m, N″CH2CH2), 4.40 (1H, dd, J = 7.2, 12.6, N′CHHCH2), 2.94 (1H, ddd, J = 7.2, 11.5, 13.5 Hz,
NCH2CHH), 2.86–2.72 (1H, overlap, NCH2CHH), 2.85–2.64 (1H, overlap, N′CH2CHH), 2.84–2.65
Page 9
S9
(2H, overlap, N″CH2CH2), 2.81 (6H, s, NMe2), 2.45 (1H, ddd, J = 7.7, 11.5, 13.3 Hz, N′CH2CHH),
2.24–2.19 (1H, overlap, NCHHCMe3), 2.24, 2.23, 2.19, 2.17, 2.16, 2.10, 2.03, 2.02, 1.98, 1.92, 1.91,
1.87 (3H × 12, s, C5Me4 × 3), 1.51 (1H, d, J = 12.4 Hz, NCHHCMe3), 0.85 (9H, s, CMe3) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.4, 130.2, 128.8, 122.6, 121.2, 120.8, 119.8, 118.6, 116.3,
115.3, 114.9, 114.0, 113.9, 113.9, 113.4 (C5Me4 × 3), 70.5 (N″CH2CH2), 67.7 (NCH2CH2), 63.7
(N′CH2CH2), 62.4 (NCH2CMe3), 45.2 (NMe2), 33.8 (CMe3), 31.2 (N′CH2CH2), 30.1 (NCH2CH2),
29.4 (N″CH2CH2), 28.3 (CMe3), 12.7, 12.3, 11.8, 11.7, 11.31, 11.27, 10.16, 10.13, 11.0, 10.89, 10.88,
10.5 (C5Me4 × 3) ppm. Anal. Calcd for C40H65N5Zr3: C, 54.00; H, 7.36; N, 7.87. Found: C, 53.75; H,
7.68; N, 7.72.
Reaction of 2 with anilines
[(LZr)(LZrNHPh)(LH2Zr)(μ-NPh)2] (6a): In the glovebox, 2 (0.014 mmol, 13.0 mg) was
dissolved in C6D6 (0.4 mL) with the internal standard. After 1H NMR spectrum was recorded, aniline
(0.049 mmol, 4.5 μL) was added under argon into the NMR tube. The reaction progress was
monitored at 25 ºC by 1H NMR analysis. After 19h, 6a was formed in 77% yield. The structure was
identified by comparison of the following partial NMR data with those of fully characterized 6b. 1H NMR (C6D6, 400 MHz): δ 7.41–7.18 (4H, m, ArH), 7.03–6.72 (7H, m, ArH), 6.62–6.50 (4H, m,
ArH), 5.43 (1H, m, NCHHCH2), 5.40 (1H, s, NHZr), 4.60 (1H, ddd, J = 2.2, 8.1, 14.7 Hz,
NCHHCH2), 4.10 (1H, dd, J = 5.1, 5.5 Hz, N′CHHCH2), 3.41 (1H, m, N′CH2CHH), 2.85 (1H, m,
N′CH2CHH), 2.79 (1H, m, NCH2CHH), 2.67 (1H, ddd, J = 2.2, 7.3, 13.7 Hz, NCH2CHH), 2.37 (1H,
m, N′CHHCH2), 2.00 (1H, m, N″HH), 2.43, 2.30, 2.16, 2.04, 1.95, 1.914, 1.910, 1.86, 1.82, 1.79,
1.78, 1.52 (3H × 12, s, C5Me4 × 3), 1.75–1.55 (3H, m, N″CHHCH2), 1.36 (1H, m, N″CHHCH2),
0.78 (1H, m, N″HH) ppm. 13C NMR (C6D6, 100 MHz): δ 160.4, 159.1, 156.0, 129.7, 134.7, 125.6,
125.3, 123.9, 122.7, 121.6, 121.3, 120.9, 120.7, 120.4, 119.3, 119.2, 118.6, 118.2, 118.1, 118.0,
117.74, 117.70, 117.3, 116.0, 115.7, 115.6, 115.0, 113.5, 111.8 (Ar and C5Me4), 71.7, 51.3, 44.3
(NCH2CH2 × 3), 30.3, 28.5, 24.1 (NCH2CH2 × 3), 14.6, 13.3, 12.5, 12.2, 11.804, 11.796, 11.6, 11.1,
11.0, 10.8, 10.1, 9.8 (C5Me4 × 3) ppm.
[(LZr){LZr(NHC6H4-4-Br)}(LH2Zr)(μ-NC6H4-4-Br)2] (6b): In the glovebox, 2 (0.011 mmol, 9.5
mg) was dissolved in C6D6 (0.5 mL) with the internal standard. After 1H NMR spectrum was
recorded, 4-bromoaniline (0.045 mmol, 7.8 mg, 4.3 equiv) was added into the NMR tube in the box.
The reaction progress was monitored at 25 ºC by 1H NMR analysis. After 72 h, 6b was formed in
87% yield. Complex 6b was also synthesized in a preparative scale since isolation of crystalline 6b
was successful. In the glovebox, 2 (0.0735 mmol, 65.6 mg) was dissolved in toluene (10 mL) with
p-bromoaniline (0.445 mmol, 76.5 mg, 6 equiv) at ambient temperature. This solution was heated at
60 °C. After heating for 24 h, the solution was cooled to room temperature and all volatiles were
removed under reduced pressure. In the box, the residue was washed with pentane and dried to give
the desired 6b (71.3 mg, 76% yield). 6b was recrystallized from toluene at −30°C.
Page 10
S10
1H NMR (C6D6, 400 MHz): δ 7.47 (1H, br, ArH), 7.35 (2H + 1H, overlap, Ar′H, ortho and ArH),
6.98 (2H, d, J = 8.8 Hz, Ar″H, ortho), 6.82 (1H, br, ArH), 6.44 (2H, d, J = 8.8 Hz, Ar′H, meta), 6.27
(1H, br, ArH), 6.18 (2H, d, J = 8.8 Hz, Ar″H, meta), 5.14 (1H, m, NCHHCH2), 5.10 (1H, s, Ar′NH),
4.45 (1H, m, NCHHCH2), 4.00 (1H, m, N′CHHCH2), 3.34 (1H, m, N′CH2CHH), 2.79 (1H, m,
N′CH2CHH), 2.71 (1H, m, NCH2CHH), 2.56 (1H, m, NCH2CHH), 2.19 (1H, overlap, N′CHHCH2),
2.28, 2.22, 2.09, 1.95, 1.84, 1.79, 1.73, 1.72, 1.684, 1.681, 1.58, 1.40 (3H × 12, s, C5Me4 × 3), 1.73
(1H, overlap, N″HH), 1.62 (1H, m, N″CH2CHH), 1.53 (1H, overlap, N″CH2CHH), 1.51 (1H,
overlap, N″CHHCH2), 1.23 (1H, m, N″CHHCH2), 0.52 (1H, m, N″HH) ppm. 13C{1H} NMR (C6D6,
100 MHz): δ 159.2 (Ar″, ipso), 158.1 (Ar, ipso), 154.7 (Ar′, ipso), 131.7 (Ar, ortho), 131.5 (Ar′,
ortho), 131.1 (Ar″, ortho), 130.9 (Ar, ortho), 126.2 (Ar, meta), 126.1 (Ar, meta), 122.1 (Ar″, meta),
120.6 (Ar′, meta), 110.2 (Ar, para), 110.1 (Ar″, para), 106.9 (Ar′, para), 135.1, 126.0, 123.1, 121.9,
120.8, 120.5, 120.2, 119.6, 118.79, 118.78, 117.9, 116.0, 115.8, 113.8, 112.1 (C5Me4 × 3), 71.5
(NCH2CH2), 51.3 (N′CH2CH2), 44.4 (N″CH2CH2), 30.1 (NCH2CH2), 28.2 (N′CH2CH2), 23.9
(N″CH2CH2), 14.4, 13.3, 12.4, 12.0, 11.8, 11.7, 11.5, 10.9, 10.84, 10.76, 10.0, 9.8 (C5Me4 × 3) ppm.
Anal. Calcd for (C51H63Br3N6Zr3)(C7H8): C, 51.01; H, 5.24; N, 6.15. Found: C, 50.73; H, 5.16; N,
6.23.
[(LZr){LZr(NHC6H4-4-OMe)}(LH2Zr)(μ-NC6H4-4-OMe)2] (6c): In the glovebox, 2 (0.011 mmol,
10.0 mg) was dissolved in C6D6 (0.4 mL) with the internal standard. After 1H NMR spectrum was
recorded, p-anisidine (0.055 mmol, 6.8 mg) was added into the NMR tube in the box. The reaction
progress was monitored at 25 ºC by 1H NMR analysis. After 24h, 6c was formed in 84% yield. The
structure was identified by comparison of the following NMR data with those of fully characterized
6b. 1H NMR (C6D6, 400 MHz): δ 7.24 (1H, d, J = 8.0 Hz, ArH), 7.10 (1H, d, J = 8.0 Hz, ArH), 7.00
(2H, d, J = 8.8 Hz, ArH, ortho), 6.91 (1H, d, J = 8.4 Hz,ArH), 6.79 (2H, d, J = 8.8 Hz, ArH, ortho),
6.59 (2H, d, J = 8.8 Hz, ArH, meta), 6.54 (1H, d, J = 8.4 Hz, ArH), 6.49 (2H, d, J = 8.8 Hz, ArH,
meta), 5.42 (1H, ddd, J = 7.2, 7.4, 14.6 Hz, NCHHCH2), 5.37 (1H, s, ArNHZr), 4.68 (1H, ddd, J =
2.2, 5.7, 14.6 Hz, NCHHCH2), 4.14 (1H, ddd, J = 1.4, 6.1, 10.6 Hz, N′CHHCH2), 3.53 (3H, s,
ArOMe), 3.46 (3H, s, ArOMe), 3.41 (1H, m, N′CH2CHH), 3.32 (3H, s, ArOMe), 2.79 (1H, m,
N′CH2CHH), 2.78 (1H, m, NCH2CHH), 2.72 (1H, ddd, J = 2.2, 7.2, 13.7 Hz, NCH2CHH), 2.46 (1H,
m, N′CHHCH2), 2.02 (1H, m, N″HH), 2.44, 2.32, 2.18, 2.06, 1.98, 1.97, 1.94, 1.89, 1.85, 1.83, 1.81,
1.56 (3H × 12, s, C5Me4 × 3), 1.75–1.44 (4H, m, N″CH2CH2), 0.89 (1H, m, N″HH) ppm. 13C{1H}
NMR (C6D6, 100 MHz): δ 154.6, 152.6, 152.54, 152.52, 151.4, 150.2, 134.3, 125.3, 125.2, 124.1,
122.7, 121.4, 120.9, 120.10, 120.05, 119.9, 119.6, 118.9, 118.3, 117.8, 117.6, 115.7, 115.6, 115.3,
114.4, 111.6, 113.8, 113.6, 113.1 (Ar and C5Me5), 71.8 (NCH2), 55.4, 55.2, 55.0 (OMe × 3), 51.2
(N′CH2), 44.3 (N″CH2), 30.0 (NCH2CH2), 28.5 (N′CH2CH2), 24.1 (N″CH2CH2), 14.5, 13.2, 12.5,
12.1, 11.8, 11.7, 11.6, 11.1, 11.0, 10.9, 10.1, 9.8 (C5Me4 × 3) ppm.
Page 11
S11
Figure S3. VT NMR spectra of 6b in toluene-d8 (aromatic region only). Solid circles
and open squares indicate Ar-H and Ar′-H (bridging imide ligands), respectively, and
solid triangles shows Ar″-H (terminal amide ligand). The asterisks denote solvent
signals.
373K
353K
333K
313K
273K
253K
233K
213K
**
*
* **
* **
* **
* **
**
*
**
*
* *
*
Zr N
Zr
N Zr
N
N
NH
Br
Br
Br
NH2
Ar
Ar
Ar
Page 12
S12
Synthesis of 7
To a solution of complex 2 (5.5 mg, 6.2 μmol) in C6D6 (0.5 mL) with the internal standard was
added 2,6-di-tert-butylphenol (2 mg, 9.7 μmol) at 25 ºC. The solution color turned from yellow to
light yellow while the reaction proceeded gradually. After 24 h, 1H NMR analysis showed that
complex 7 was formed quantitatively. The reaction was either carried out in toluene, and 7 was
recrystallized from toluene-pentane. The structure was determined by NMR and XRD analysis, and
the following NMR assignment was made by COSY, HMQC, and HMBC experiments.
[(LZrNMe2)2(LZrOC6H3-2,6-t-Bu2)] (7): 1H NMR (C6D6, 400 MHz): δ 7.32 (1H, dd, J = 1.6, 7.6
Hz, ArH), 7.27 (1H, dd, J = 1.6, 7.6 Hz, ArH), 6.81 (1H, t, J = 7.6 Hz, ArH), 5.03 (1H, dt, J = 5.8,
12.0 Hz, NCHHCH2), 4.97–4.87 (2H, m, N′CHHCH2 and N″CHHCH2), 4.67 (1H, dd, J = 7.4, 12.4
Hz, N′CHHCH2), 4.61 (1H, td, J = 4.0, 12.4 Hz, N″CHHCH2), 4.41 (1H, dd, J = 7.6, 12.0 Hz,
NCHHCH2), 3.07 (6H, s, NMe2), 2.94 (1H, ddd, 7.6, 12.0, 13.2 NCH2CHH), 2.83 (1H, ddd, J = 7.4,
12.0, 13.4 Hz, N′CH2CHH), 2.68 (6H, s, NMe2), 2.64 (1H, dd, J = 5.6, 13.4 Hz, N′CH2CHH), 2.58
(2H, m, N″CH2CH2), 2.51 (1H, dd, J = 5.8, 13.2 Hz, NCH2CHH), 2.31, 2.26, 2.24, 2.05, 1.97, 1.97,
1.97, 1.94, 1.93, 1.93, 1.87, 1.81 (3H × 4 × 3, s, C5Me4), 1.64 (9H, s, t-Bu), 1.53 (9H, s, t-Bu) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 163.1 (OAr-1), 138.2, 136.9 (OAr-2,6), 128.5, 125.1 (OAr-3,5),
117.8 (OAr-4), 130.0, 128.1, 127.7, 125.5, 124.4, 122.0, 121.6, 121.3, 119.6, 119.4, 116.3, 116.2,
115.7, 115.7, 115.3 (C5Me4 × 3), 67.3, 67.0, 61.0 (NCH2 × 3), 50.3 (NMe2), 49.6 (NMe2), 37.1
(CMe3), 35.81 (CMe3), 35.78 (CMe3), 32.4 (CMe3), 29.8, 29.7, 29.4 (NCH2CH2 × 3), 14.3, 13.8,
12.9, 12.7, 12.2, 12.0, 11.9, 11.7, 11.6, 11.2, 10.5, 10.0 (C5Me4 × 3) ppm.
Reaction of 8 with neo-PenNH2
{Me2Si(C5Me4)(Nt-Bu)}Zr(NMe2)2 (8) (30 μmol, 13 mg) was dissolved in C6D6 (0.4 mL) with
(Me3Si)2CH2 as an internal standard. A solution of neo-PenNH2 in C6D6 (1.2 M, 70 μL) was added at
25 °C. The reaction in the sealed NMR tube was monitored by 1H NMR analysis. The reaction
reached the equilibrium in 5 h. The conversion of 8 (98.6%) and yields of 9–11 (30.8%, 42.1%, and
12.8% yield, respectively) were estimated based on the integration ratios of singlet signals for t-Bu
groups and the internal standard although the rest of quite minor products (13%) could not be
identified. Thus, the existing molar ratios of 8:9:10:11 were calculated from the above
1.6:35.4:48.3:14.7 (at 5 h) and 1.6:36.6:48.1:13.7 (at 28 h). However, after removal of volatiles, 1H
NMR spectrum indicated that the molar ratio changed to 0.9:26.1:72.3:0.7. neo-PenNH2 (1.2 M in
C6D6, 40 μL) was added to the sample containing complex 10 as the major, and 1H NMR analysis of
the resultant solution showed an increased ratio of 11: the complex distribution of 8:9:10:11 =
~0:7.8:70.7:21.5. These complexes were not attempted to isolate because they were waxy. The
structure of the major 10 was clearly determined by 1H and 13C NMR analysis while the structures of
minor 9 and 11 were proposed by 1H NMR analysis.
Page 13
S13
The 1H NMR spectra of 9 and 10 showed signals for amido NH (triplet-like doublet of doublet) and
diastereotopic α-methylene protons (multiplet or doublet of doublet) whereas a doublet signal for
α-methylene protons and high-field shifted singlet signals for t-BuN and SiMe2 groups were
observed in the spectrum of 11, indicative of different environment of the supporting ligand from
that of 9 or 10.
[{Me2Si(C5Me4)(Nt-Bu)}Zr(NMe2)(NHCH2CMe3)] (9): 1H NMR (C6D6, 400 MHz): δ 3.58 (1H,
t-like dd, J = 7.2, 8.4 Hz, NH), 3.26–3.21 (2H, m, NHCH2), 2.83 (6H, s, NMe2), 2.14, 2.09, 1.99,
1.83 (3H × 4, s, C5Me4), 1.38 (9H, s, Nt-Bu), 0.89 (9H, s, NHCH2CMe3), 0.66 (3H, s, SiMeMe), 0.63
(3H, s, SiMeMe) ppm.
[{Me2Si(C5Me4)(Nt-Bu)}Zr(NHCH2CMe3)2] (10): 1H NMR (C6D6, 400 MHz): δ 3.40 (2H, t-like
dd, J = 7.6, 9.6 Hz, NH), 3.20 (2H, dd, J = 9.6, 12.4 Hz, NCHH), 3.08 (2H, dd, J = 7.6, 12.4 Hz,
NCHH), 2.15, 1.97 (6H × 2, s, C5Me4), 1.42 (9H, s, Nt-Bu), 0.90 (18H, s, NHCH2CMe3), 0.64 (6H, s,
SiMe2) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 127.5, 124.7, 100.3 (C5Me4), 62.2 (NHCH2), 54.8
(NCMe3), 35.2 (NCMe3), 33.6 (NHCH2CMe3), 27.5 (NHCH2CMe3), 13.9, 11.3 (C5Me4), 7.7 (SiMe2)
ppm.
[{Me2Si(C5Me4)(NHt-Bu)}Zr(NHCH2CMe3)3] (11): 1H NMR (C6D6, 400 MHz): δ 3.68 (3H, t, J =
8.8 Hz, NH), 3.30 (6H, d, J = 8.8 Hz, NHCH2), 2.28, 1.93 (6H × 2, s, C5Me4), 1.17 (9H, s, Nt-Bu),
0.97 (27H, s, NHCH2CMe3), 0.55 (6H, s, SiMe2) ppm.
Figure S4. Crystal Structure of 3a (ellipsoids set at 40% probability. Hydrogen atoms except amide
protons are omitted for clarity).
Zr3
Zr1
Zr2
H6
N7
N6
N5
N4
N3
N2
N1
H3
H2
H5
H7
C6
C5
C4
C3C2
C1
C7
C8
C9
C10
C11
C12
C13C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24C25
C26
C27
C28
C29
C30
C31C32
C33
C34
C35
C37
C36
C38
C39
C40
C41
C42
C43
C44
C45
Page 14
S14
Figure S5. Crystal Structure of 4a (ellipsoids set at 40% probability. Hydrogen atoms except amide
protons are omitted for clarity).
Figure S6. Crystal Structure of 5 (ellipsoids set at 40% probability. Hydrogen atoms are omitted for
clarity).
Zr1
Zr2
Zr3
N3
N2
N1
N4
N5
N6
H6
H2
C1
H5
C2
C3
C4
C5
C6
C7
C8
C9
C10 C11
C12C16
C13C14
C15
C17C18
C19
C20
C21
C22
C23
C24
C25
C26
C27C28
C29 C30
C31
C32
C33
C34
C36 C35
C37
C38
C39
C40
C41
C42
Zr1
Zr2
Zr3
N1
N2
N3
N4
N5
C1C2
C3C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21C22
C23
C24
C25
C26
C27
C28
C29C30
C31 C32
C33
C34
C35
C36
C37
C38
C39
C40
C21A
C20A
C19A
C18A
C17A
C12A
C13A
C14A
C15A
C16A
Page 15
S15
Figure S7. Crystal Structure of 7 (ellipsoids set at 40% probability. Hydrogen atoms and solvent
molecule are omitted for clarity).
Zr2
N3
Zr1
Zr3
N1
N2
N4
N5
O1
C1
C2 C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C22C21
C13
C14
C15
C16
C17
C18
C19
C20
C23C24
C25C26
C27
C28
C29
C30
C31
C32
C33
C34
C35
C36
C37
C38
C39
C40
C41
C42
C43
C44
C45
C46
C47C48
C49C50
C51
Page 16
S16
Figure S8. Representation of Effective Volumes (Veff) for Two Adjacent NMe2 Groups in The
Solid-State Structures of Reported Half-zirconocene Bis(amide)s, Me2Si(C5Me4)(E)Zr(NMe2)2 [E =
Nt-Bu (a), NCHMePh (b), NC6H4-4-CH=CH2 (c), N(2-Py) (d), C2B10H2 (e)] and Cp*(L)Zr(NMe2)2
[L = salicyloxazoline (f), (g)].
50.2 Å3 46.0 Å3
47.2 Å336.9 Å3
39.7 Å3
Zr Zr Zr
ZrZr
(a) (b) (c)
(d) (e)
molecule 133.4 Å3
molecule 233.4 Å3
molecule 134.5 Å3
molecule 230.6 Å3
(g) L = 2,4-di-tert-butyl-6-(4-(tert-butyl)-4,5-dihydrooxazol-2-yl)phenoxide
Zr1
Zr2
Zr1Zr2
Zr2
Zr1Zr2
Zr1
(f) L = 2,4-di-tert-butyl-6-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenoxide
Page 17
S17
Thermolysis of 3 and 4
A mixture of 3a and 4a (57:43), prepared by reaction of 2 (13.4 µmol, 12 mg) and n-PrNH2 (77
µmol) in toluene followed by evaporation of volatiles, was dissolved in toluene (0.5 mL). The
mixture was heated at 100 ºC for 2 h. Volatiles were removed soon after the mixture was cooled to
room temperature. The product was dissolved in small amount of pentane while the solution became
red. Slow evaporation of pentane gave orange micro-crystals (8 mg, 68% yield). Formation of 12a
and 12a′ (~3.3:1) was confirmed by 1H NMR analysis. The equilibrium between 12a and 12a′ was
established by a SST experiment (Figure S9): Irradiation of signals of 12a at δ = 5.39 and –2.19 ppm
resulted in disappearance of the corresponding signals of 12a′ at δ = 5.59 and –0.95 ppm,
respectively.
[{LZr(η2-NCHCH2CH3)}(LZr)(LHZr)(μ-NHPr)] (12a): 1H NMR (C6D6, 400 MHz): δ 5.39 (1H,
dd, J = 6.8, 13.2 Hz, NCHHCH2C5Me4), 4.96–4.90 (1H, overlap, N′CHHCH2C5Me4), 4.95–4.86 (1H,
overlap, NCHHCH2C5Me4), 4.43 (1H, m, N′CHHCH2C5Me4), 3.31 (1H, m, NCH2CHHC5Me4), 2.85
(1H, m, HN″CHHCH2C5Me4), 2.84–2.76 (1H, overlap, HN1CHHCH2CH3), 2.82–2.72 (2H, overlap,
N′CH2CH2C5Me4), 2.81–2.71 (1H, overlap, NCH2CHHC5Me4), 2.45–2.37 (1H, overlap,
HN″CH2CHHC5Me4), 2.38–2.29 (1H, overlap, HN1CHHCH2CH3), 2.44, 2.33, 2.26, 2.22, 2.18, 2.13,
2.03, 2.03, 1.95, 1.93, 1.82, 1.80 (3H × 12, s, C5Me4 × 3), 2.24–2.01 (1H, overlap,
HN″CHHCH2C5Me4), 2.23–2.10 (1H, overlap, HN″CH2CHHC5Me4), 2.22–2.13 (1H, overlap,
N2CHCHHCH3), 2.15–2.09 (1H, overlap, N2CHCH2CH3), 1.35–1.10 (2H, m, HN1CH2CH2CH3),
1.15 (3H, t, J = 6.8 Hz, N2CH2CH2CH3), 0.90 (3H, t, J = 7.2 Hz, HN1CH2CH2CH3), 0.44 (1H, dd, J
= 2.8, 11.6 Hz, HN1CH2CH2CH3), 0.31 (1H, m, N2CHCHHCH3), –2.19 (1H, dd, J = 3.2, 13.2 Hz,
HN″CH2CH2C5Me4) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.2, 130.4, 126.6, 119.0, 118.9,
118.6, 118.4, 116.7, 116.3, 114.8, 114.7, 114.3, 114.2, 114.1, 113.9 (C5Me4 × 3), 91.2
(N2CHCH2CH3), 72.1 (NCH2CH2C5Me4), 65.1 (N′CH2CH2C5Me4), 55.6 (HN1CH2CH2CH3), 52.6
(HN″CH2CH2C5Me4), 38.6 (N2CHCH2CH3), 32.5 (HN1CH2CH2CH3), 31.3 (HN″CH2CH2C5Me4),
30.7 (NCH2CH2C5Me4), 30.3 (N′CH2CH2C5Me4), 19.5 (N2CHCH2CH3), 12.5 (HN1CH2CH2CH3),
13.0, 12.0, 11.6, 11.5, 11.13, 11.12, 11.0, 10.9, 10.8, 10.4, 10.4, 10.0 (C5Me4 × 3) ppm.
12a′: 1H NMR (C6D6, 400 MHz): δ 5.59 (1H, m), 5.01−4.84 (1H, overlap), 4.90−4.79 (1H, overlap),
4.60−4.45 (2H, m), 3.22−3.06 (2H, m), 2.83−2.74 (overlap), 2.31, 2.28, 2.24, 2.22, 2.21, 2.18, 2.14,
2.13, 1.99, 1.97, 1.86, 1.80 (3H × 12, s, C5Me4 × 3), 2.26−2.16 (overlap), 2.15−2.10 (1H, overlap,
η2-NCH), 1.21−1.13 (overlap), 0.52 (1H, m), −0.95 (1H, dd, J = 3.6, 14.4 Hz, NH) ppm. 13C{1H}
NMR (C6D6, 100 MHz): δ 131.7, 119.5, 118.9, 118.8, 117.7, 116.7, 116.6, 115.3, 115.2, 114.6, 114.4,
113.5 (C5Me4), 89.0 (η2-NCH), 71.9, 65.3, 56.6, 53.0 (NCH2), 38.9, 34.4, 32.4, 30.6, 30.4 (NCCH2),
19.1, 13.1, 12.7, 12.05, 12.01, 11.7, 11.4, 11.3, 11.2, 10.8, 10.5, 10.4, 10.2, 10.2 (C5Me4, NCCCH3)
ppm.
Page 18
S18
Figure S9. 1H NMR spectra in the SST experiment (C6D6, 70 ºC): lower field region (a) before and
(b) after irradiation at δ = 5.39 ppm (signal for NCHHCH2C5Me4 of 12a), and higher field region (c)
before and (d) after irradiation at δ = –2.19 ppm (signal for HN″CH2CH2C5Me4 of 12a).
Zr N H
Zr
N Zr
N
H
H
H
H
H
H
1.93
2.182.03
2.44
2.85
2.24-2.01
2.131.82
2.322.22
2.03
1.802.26
1.95
5.39
4.95-4.86
4.43
4.96-4.90
2.82-2.72HH
HH
3.31,2.81-2.71
H H
2.45-2.372.23-2.10(a) (b)
-2.19Zr N H
Zr
N Zr
N
H
H
H
H
H
H
HH
HH
H H
NHN
1.80
2.26
1.15
0.90
0.44
2.22
-2.19
4.95-4.86
Figure S10. The most plausible structure of 12a: (a) assignment of resonances of the supporting
ligands (green) and their arrangement by HSQC, HMBC, and ROESY (blue arrows), and (b)
arrangement of other ligand fragments by ROESY (blue arrows).
5.00 4.505.50
irradiation
-1.50 -2.00 -2.50-0.500.50 0.00 -1.00
irradiation
(a)
(c)
(b)
(d)
Page 19
S19
[{LZr(η2-NCHCH3)}(LZr)(LHZr)(μ-NHEt)] (12b): 1H NMR (C6D6, 400 MHz): δ 5.42 (1H, ddd,
J = 1.6, 8.0, 12.8 Hz, NCHHCH2C5Me4), 4.99–4.87 (1H, overlap, NCHHCH2C5Me4), 4.96–4.85 (1H,
overlap, N′CHHCH2C5Me4), 4.50–4.38 (1H, overlap, N′CHHCH2C5Me4), 3.38–3.26 (1H, m,
NCH2CHHC5Me4), 2.95–2.93 (1H, m, HN1CHHCH3), 2.89–2.80 (1H, m, HN″CHHCH2C5Me4),
2.86–2.76 (2H, overlap, N′CH2CH2C5Me4), 2.84–2.73 (1H, overlap, NCH2CHHC5Me4), 2.42–2.35
(1H, overlap, HN″CH2CHHC5Me4), 2.45, 2.36, 2.31, 2.20, 2.19, 2.10, 2.06, 2.03, 1.94, 1.92, 1.82,
1.80 (3H × 12, s, C5Me4 × 3), 2.42–2.32 (1H, overlap, HN1CHHCH3), 2.27–2.17 (1H, overlap,
N2CHCH3), 2.25–2.19 (1H, overlap, HN″CH2CHHC5Me4), 2.15–1.94 (1H, overlap,
HN″CHHCH2C5Me4), 1.46 (3H, d, J = 6.0 Hz, N2CHCH3), 0.97 (3H, t, J = 7.0 Hz, HN1CH2CH3),
0.24 (1H, dd, J = 2.8, 11.6 Hz, HN1CH2CH3), –2.20 (1H, dd, J = 3.2, 14.0 Hz, HN″CH2CH2C5Me4)
ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.1, 130.3, 126.8, 119.2, 119.1, 118.9, 118.4, 116.8,
116.5, 115.4, 115.0, 114.54, 114.51, 114.1, 113.8 (C5Me4 × 3), 80.9 (N2CHCH3), 72.0
(NCH2CH2C5Me4), 64.9 (N′CH2CH2C5Me4), 52.4 (HN″CH2CH2C5Me4), 47.3 (HN1CH2CH3), 31.3
(HN″CH2CH2C5Me4), 30.6 (NCH2CH2C5Me4), 30.4 (N′CH2CH2C5Me4), 29.9 (N2CHCH3), 24.2
(HN1CH2CH3), 13.1, 12.0, 11.7, 11.6, 11.5, 11.17, 11.16, 11.14, 11.08, 11.0, 10.2, 10.1 (C5Me4 × 3)
ppm.
12b′: Partial 1H NMR (C6D6, 400 MHz): δ 5.66 (1H, m), 4.96 (1H, overlap), 4.82 (1H, m), 4.57 (1H,
td, J = 8.0, 12.8 Hz), 4.01 (1H, dd, J = 6.8, 12.0 Hz), 3.71 (1H, dd, J = 7.2, 12.0 Hz), 3.17 (1H, td, J
= 8.0, 13.2 Hz), 2.85–2.75 (overlap), 2.72–2.60 (overlap), 2.37, 2.31, 2.28, 2.22, 2.21, 2.15, 2.04,
1.99, 1.97, 1.85, 1.84, 1.81 (3H × 12, s, C5Me4 × 3), 2.35–2.25 (1H, overlap, NCHCH3), 2.28–2.14
(overlap). 1.57 (3H, d, J = 6.0 Hz, NCHCH3), 1.20–1.15 (overlap), 1.01 (3H, t, J = 7.2 Hz,
NCH2CH3), –0.91 (1H, dd, J = 3.2, 14.0 Hz, NH) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 131.3,
130.8, 127.2, 119.7, 119.5, 117.9, 117.1, 116.8, 116.6, 115.23, 115.16, 114.9, 114.4, 113.7 (C5Me4 ×
3), 78.6 (NCHCH3), 71.9 (NCH2), 65.1 (NCH2), 53.2 (NCH2), 48.3 (NCH2), 31.4 (NCH2CH2), 30.6
(NCH2CH2), 30.5 (NCH2CH2), 30.2 (NCHCH3), 23.9 (NCH2CH3), 13.2, 12.1, 11.9, 11.65, 11.58,
11.4, 11.3, 11.2, 11.1, 10.5, 10.3, 10.2 (C5Me4 × 3) ppm.
Synthesis of 13c and 14a
Substrate 13c was synthesized via Gabriel method:
A solution of 3,3-dimethyl-1-propyne (15 mmol, 1.84 mL) in THF (20 mL) was cooled to –78 °C
under argon, and a solution of BuLi (2.5 M in hexane, 6.3 mL) was added. After stirred at –78 °C for
Page 20
S20
15 min and at 0 °C for 0.5 h, 1,3-diiodopropane (17.4 mmol, 2.0 mL) and HMPA (3.0 mL) were
added at –78 °C. The mixture was allowed to slowly warm to room temperature and stirred for 8 h.
After workup, the crude monoiodide was obtained by distillation (76–78 °C /0.001 MPa) (2.5 g, 69%
purity).
The monoiodide (~6 mmol, 1.6 g) and potassium phthalimide (8.5 mmol, 1.6 g) were dissolved in
DMF (10 mL). The mixture was heated at 145 °C for 20 h. The resultant mixture, after cooled to
room temperature, was dropped into a vigorously stirred ice water, giving white precipitate. The
precipitate was obtained by filtration, washed with H2O, and air-dried (1.1 g). The solid was
dissolved in MeOH (20 mL) and H2NNH2•H2O (17 mmol, 0.85 g) was added. The mixture became
suspended while it was heated at reflux for 1 h. The insoluble solid was removed by filtration, and
the product was separated by extraction under acidic and basic conditions. Distillation of the
colorless oil at 90–110 °C/0.0016 MPa gave 13c (0.10 g, 12% yield for the monoiodide). 1H NMR
(CDCl3, 400 MHz): δ 2.77 (2H, t, J = 7.0 Hz, NCH2), 2.19 (2H, t, J = 7.0 Hz, NCH2CH2CH2) 1.59
(2H, quint-like tt, J = 7.0 Hz, NCH2CH2CH2), 1.23 (2H, br, NH2), 1.17 (9H, s, CMe3) ppm. 1H NMR
(C6D6, 400 MHz): δ 2.55 (2H, t, J = 7.0 Hz, NCH2), 2.11 (2H, t, J = 7.0 Hz, NCH2CH2CH2) 1.40
(2H, quint-like tt, J = 7.0 Hz, NCH2CH2CH2), 1.22 (9H, s, CMe3), 0.41 (2H, br, NH2) ppm. 13C{1H}
NMR (CDCl3, 100 MHz): δ 89.4 (CH2C≡C), 77.7 (CH2C≡C), 41.3 (NCH2), 32.9 (NCH2CH2), 31.3
(CMe3), 27.3 (CMe3), 16.1 (CH2C≡C) ppm.
Synthesis of 14a is outlined as follows:
4-Cyano-4-methyl-1-pentyne (7.5 mmol, 0.80 g)5 was dissolved in THF (15 mL) under nitrogen
atmosphere. The solution was cooled to –78 °C, and a solution of BuLi in hexane (2.5 M, 8.8 mmol)
was added. After stirring at this temperature for 0.5 h and at 0 °C for 10 min, HMPA (2.0 mL) and
iodoethane (8.8 mmol, 0.71 mL) were added subsequently. The mixture was allowed to warm to
room temperature and continued to stir for 8 h. The reaction was then quenched by addition of
ice-water. The product was extracted with ether, and ethereal layer was washed with H2O. The
organic layer was dried over Na2SO4. Evaporation of solvent and distillation at 78–82 °C/21 mbar
gave the desirable nitrile as a colorless oil (0.67 g, 62%). 1H NMR (CDCl3, 400 MHz): δ 2.44 (2H, t,
J = 2.4 Hz, CH2C≡C), 2.21 (2H, tq, J = 2.4, 7.6 Hz, CH2CH3), 1.42 (6H, s, NCCMe2), 1.15 (3H, t, J
= 7.6 Hz, CH2CH3) ppm. 13C NMR (CDCl3, 100 MHz): δ 124.5 (s, CN), 86.0 (s, C≡C), 73.5 (s,
C≡C), 32.5 (s, CCN), 31.4 (t, J = 134 Hz, CH2), 25.9 (q, J = 130 Hz, CMe2), 14.1 (q, J = 128 Hz,
CH2CH3), 12.4 (t, J = 131 Hz, CH2CH3) ppm.
5 Stevens, R. V.; DuPree, Jr., L. E.; Edmonson, W. L.; Magid, L. L.: Wentland, M. P. J. Am. Chem. Soc. 1971, 93, 6637.
Page 21
S21
LiAlH4 (5.3 mmol, 0.20 g) was suspended in Et2O (15 mL) under nitrogen atmosphere. The above
nitrile (4.4 mmol, 0.60 g) was addd at 0 °C in 10 min. The mixture was warmed to r.t. and then
heated to reflux. After 3 h, the reaction mixture was allowed to cool to 0 °C. Na2SO4 (22 mmol, 3.10
g) and NaF (22 mmol, 0.92 g) were added with stirring, subsequently, H2O (0.3 mL) was syringed in
carefully. After filtration of the slurry, the filtrate was treated with HCl. The ethereal layer was
removed by decantation, and the residue was washed with hexane. The residue was basified with aq.
NaOH and the product was extracted with hexane. The organic layer was separated and dried over
NaOH pellets. Most of the solvent was removed under reduced pressure (25 °C/80 mbar). The
desirable 14a was distilled at 70 °C/20 mbar (0.12 g, 20%). 1H NMR (CDCl3, 400 MHz): δ 2.53 (2H,
s, CH2N), 2.15 (2H, dq, J = 2.4, 4.8 Hz, CH2CH3) 2.04 (2H, t, J = 2.4 Hz, CH2C≡C), 1.25 (2H, br,
NH2), 1.11 (3H, t, = 4.8 Hz, CH2CH3), 0.91 (6H, s, CCMe2) ppm.
Catalytic Cyclization of Aminoalkynes 13 and 14
In the glovebox, complex 2 (2.5–4.7 μmol) was weighed into the NMR tube with a Teflon valve. The
sample was dissolved in C6D6 (0.45 mL) with (Me3Si)2CH2 (trace amount) as an internal standard. A
solution of the aminoalkyne (0.59–1.30 M in C6D6, ca 20 equiv) was syringed into the NMR tube.
NMR spectra were also recorded before addition of the substrate and heating the sample tube to
monitor the reaction progress. The products 15a, 15b, and 16b were identified by 1H NMR spectra
reported in the literature.6 The novel cyclization products 15c and 16a were identified by spectral
comparison with those analogs, respectively.
5-Neopentyl-3,4-dihydro-2H-pyrrole (15c): 1H NMR (C6D6, 400 MHz): δ 3.77 (2H, quint-t-like ttt,
J = 1.8, 7.2 Hz, NCH2), 2.15 (2H, br, CCH2CMe3), 2.07 (2H, tt, J = 1.8, 7.8 Hz, N=CCH2), 1.44 (2H,
tt, J = 7.2, 7.8 Hz, NCH2CH2CH2), 1.01 (9H, s, CMe3) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ
174.9 (N=C), 61.5 (NCH2CH2CH2), 46.9 (CH2CMe3), 40.1 (NCH2CH2CH2), 31.3 (CH2CMe3), 30.2
(CH2CMe3), 23.1 (NCH2CH2CH2) ppm.
3,3-Dimethyl-5-propyl-3,4-dihydro-2H-pyrrole (16a): 1H NMR (C6D6, 400 MHz): δ 3.55 (2H,
quintet-like tt, J = 1.6 Hz, NCH2), 2.12 (2H, dt, J = 1.6, 7.2 Hz, CH2CH2CH3), 1.93 (2H, t, J = 1.6
Hz, N=CCH2) 1.59 (2H, sextet-like dq, J = 7.2 Hz, CH2CH2CH3), 0.89 (3H, t, J = 7.2 Hz,
CH2CH2CH3), 0.87 (6H, s, CMe2) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 175.8 (N=C), 74.8
(CH2N=C), 52.4 (N=CCH2), 38.3 (CMe2), 36.3 (CH2CH2CH3), 28.0 (CMe2), 19.9 (CH2CH2CH3),
14.2 (CH2CH2CH3) ppm.
6 (a) McGrane, P. L.; Jensen, M.; Livinghouse, T. J. Am. Chem. Soc. 1992, 114, 5459. (b) Kondo, T.; Okada, T.; Mitsudo, T. J. Am. Chem. Soc. 2001, 124, 186.
Page 22
S22
Figure S11. 1H NMR spectra (C6D6, t = 0.5 h, δ = 4.90–2.85 ppm) when complex 2 and excess
amounts of 13 were mixed at 25 °C; (a) with 13a, (b) with 13b, and (c) with 13c.
Stoichiometric Reaction of 2 and 13c
(i) Characterization of 17
Complex 2 (5.6 μmol, 5.0 mg) and 13c (42 μmol, 7.5 equiv) were dissolved in C6D6 (0.5 mL) at
25 °C, and the reaction was monitored by 1H NMR analysis. As observed in the reaction with
n-PrNH2 or catalytic reaction at 25 °C, the 1H NMR spectrum recorded at the initial stage (0.5 h)
showed quantitative formation of the kinetically favored structure (17ckinetic), containing four
molecules of 13c. After 20 h, this turned to the thermodynamically stable structure (17c). These two
structures were characterized only by NMR spectroscopy, and isolation of 17c was not attempted.
17ckinetic (t = 0.5 h at 25 °C): Partial 1H NMR (C6D6, 400 MHz): δ 4.74–4.65 (2H, m), 4.35 (1H, dd, J
= Hz), 3.96–3.88 (1H, m), 3.71–3.46 (3H, m), 3.44–3.26 (3H, m), 3.26–2.87 (5H, m), 2.80–2.68 (1H,
m), 2.51–2.48 (1H, m), 2.35 (4H, m), 2.28, 2.20, 2.20, 2.15, 2.14, 2.12, 2.05, 1.961, 1.955, 1.95,
1.933, 1.927 (3H × 12, s, C5Me4 × 3), 1.74–1.62 (8H, m), 1.304, 1.302, 1.284, 1.281 (9H × 4, s,
CMe3 × 4), 0.88 (1H, m), 0.75 (1H, m), 0.29 (1H, m) ppm.
[(LZrNHR)(LHZrNHR)(LHZr)(μ-NHR)(μ3-NR)] (R = CH2CH2CH2C≡CBu-t) (17c) (t = 20 h at
25 °C): Following partial signal assignment was made by COSY, HMQC, and HMBC experiments.
Partial 1H NMR (C6D6, 400 MHz): δ 4.45 (1H, dd, J = 7.2, 12.0 Hz, NCHH), 4.37 (1H, t-like dd, J =
8.0 Hz, NH), 4.25 (1H, dd, J = 4.6, 11.8 Hz, NH), 4.08 (1H, t-like dd, J = 11.6 Hz, NCHH), 3.95 (2H,
m, NCH2), 3.81 (1H, m, NCHH), 3.65–3.45 (5H, m, NCH2 + NCCH2), 3.37 (2H, m, NCH2), 2.93
(2H, m, NCH2), 2.50–2.20 (2H × 4, m, NCH2CH2CH2), 2.29, 2.23, 2.20, 2.16, 2.15, 2.14, 2.14, 2.10,
(a)
(b)
(c)
Page 23
S23
2.05, 1.96, 1.91, 1.87 (3H × 12, s, C5Me4 × 3), 1.95–1.55 (8H, m, NCH2CH2CH2), 1.31, 1.30, 1.29,
1.28 (9H × 4, s, CMe3 × 4), 0.87 (1H, m), 0.73 (1H, dd, J = 6.6, 12.6 Hz), 0.32 (1H, t-like dd, J = 7.0
Hz, NH) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 129.7, 128.7, 122.4, 122.2, 118.5, 118.1, 117.74,
117.69, 116.7, 116.4, 116.2, 115.4, 115.0, 114.5, 113.8 (C5Me4 × 3), 89.5, 89.0, 88.84, 88.78
(CH2C≡C × 4), 79.6, 79.2, 78.9, 77.9 (CH2C≡C × 4), 63.1, 60.2, 57.5, 55.7, 53.0, 51.8, 51.2
(NCH2CH2C5Me4 × 3 + NCH2CH2CH2 × 4), 36.40, 36.37, 36.3, 35.8 (NCH2CH2CH2 × 4), 31.83,
31.81, 31.79, 31.7 (CMe3 × 4), 31.4, 31.2, 28.7 (NCH2CH2C5Me4 × 3), 27.7, 27.6 (CMe3 × 4), 18.7,
18.0, 17.2, 17.1 (CH2C≡C × 4), 13.3, 13.3, 13.2, 12.5, 12.03, 12.00, 11.9, 11.7, 11.6, 11.4, 11.3, 10.9
(C5Me4 × 3) ppm.
Figure S12. Partial 1H NMR spectra of the reaction of 2 and 13c (C6D6, 25 °C): Open circles and
solid triangles indicate signals for C5Me4 groups in 17ckinetic and 17c, respectively.
4.50 4.00 3.50 3.00 2.30 2.20 2.00 1.902.10
Me2NH
t = 0.5 h
t = 20 h
13c
Page 24
S24
Figure S13. Comparison of 1H NMR partial spectra of complexes 3a and 17c (C6D6, 25 °C):
Characteristic NCH2 and terminal NH protons are indicated in red and blue, respectively.
(ii) Thermolysis of 17c
Complexes 18c (and 18c′) were synthesized by thermolysis of 17c analogously for the synthesis of
12 (and 12′). First, stoichiometric reaction of 2 (16.8 μmol, 15 mg) with 13c (5 equiv) was carried
out in toluene. After the solution was stood at 25 °C for 21 h, all volatiles were removed under
reduced pressure, and the residue was dissolved in C6D6 and 17c was found to be the major product.
The solution was heated at 100 °C for 1 h while the solution became orange. 1H NMR analysis of the
mixture showed formation of complex 18c (81% yield), 18c′ (19% yield), and 15c (~200% yield
based on complex 17c). Evaporation of volatiles and dryness in vacuo gave a mixture of 18c and
18c′ as a waxy oil (18c/18c′ = 4.3:1). The NMR signal assignment was made by COSY, HSQC, and
HMBC experiments and the structure of major 18c was determined by comparison of the NMR
spectra with those of 12a.
[{LZr(η2-NCHCH2CH2C≡CBu-t)}(LZr)(LHZr)(μ-NHCH2CH2CH2C≡CBu-t)] (18c): 1H NMR
(C6D6, 400 MHz): δ 5.34 (1H, dd, J = 7.6, 12.8 Hz, NCHHCH2C5Me4), 4.92 (1H, m,
N′CHHCH2C5Me4), 4.81 (1H, m, NCHHCH2C5Me4), 4.48−4.35 (1H, overlap, N′CHHCH2C5Me4),
3.25 (1H, m, NCH2CHHC5Me4), 3.00 (1H, m, HN1CHHCH2CH2), 2.85 (1H, m,
HN″CHHCH2C5Me4), 2.81−2.72 (2H, overlap, N′CH2CH2C5Me4), 2.75−2.65 (1H, overlap,
NCH2CHHC5Me4), 2.50−2.34 (1H, overlap, N2CHCHHCH2), 2.36−2.22 (1H, overlap,
ppm (t1)2.002.503.003.504.004.50
1H + 1H 1H 2H1H 1H × 3+ 2H
1H 1H 1H 1H 1H
1H 1H 1H 2H1H 2H 1H 5H 2H
▢
*
▢▴
containing 13c (▢) and HNMe2 (▴)
▴
containing H2NPr (*) and HNMe2 (▴)
Page 25
S25
HN1CHHCH2CH2), 2.32−2.22 (1H, overlap, N2CHCH2CH2), 2.30−2.09 (1H, overlap,
HN″CHHCH2C5Me4), 2.28−2.20 (1H, overlap, HN″CH2CHHC5Me4), 2.20−2.11 (1H, overlap,
HN″CH2CHHC5Me4), 2.17−2.12 (4H, overlap, HN1CH2CH2CH2 and N2CHCH2CH2), 2.42, 2.27,
2.26, 2.23, 2.22, 2.10, 2.03, 2.03, 1.94, 1.90, 1.85, 1.81 (3H × 12, s, C5Me4 × 3), 1.58−1.47 (1H,
overlap, HN1CH2CHHCH2), 1.42−1.25 (1H, overlap, HN1CH2CHHCH2), 1.28, 1.27 (9H × 2, s,
CMe3 × 2), 0.58 (1H, m, N2CHCHHCH2), 0.37 (1H, dd, J = 2.9, 11.8 Hz, HN1CH2CH2CH2), –2.19
(1H, m, HN″CH2CH2C5Me4) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.2, 130.6, 126.7, 119.3,
119.1, 118.8, 118.5, 116.9, 116.4, 115.1, 115.0, 114.5, 114.3, 114.3, 114.2 (C5Me4 × 3), 89.3, 89.1
(CH2C≡C × 2), 87.9 (N2CHCH2CH2), 79.9, 79.0 (CH2C≡C × 2), 72.3 (NCH2CH2C5Me4), 65.1
(N′CH2CH2C5Me4), 52.7 (HN″CH2CH2C5Me4 and HN1CH2CH2CH2), 45.3 (N2CHCH2CH2), 39.1
(HN1CH2CH2CH2), 31.8, 31.7 (CMe3 × 2), 31.2 (HN″CH2CH2C5Me4), 30.6 (NCH2CH2C5Me4), 30.2
(N′CH2CH2C5Me4), 27.70, 27.68 (CMe3 × 2), 17.5 (CH2C≡C × 2), 13.0, 12.0, 11.6, 11.5, 11.4, 11.09,
11.08, 11.02, 10.98, 10.9, 10.5, 10.0 (C5Me4 × 3) ppm.
Figure S14. Comparison of 1H NMR partial spectra of complexes 12a and 18c (C6D6, 25 °C):
Characteristic NCH2(support) and bridging NH protons are indicated in red and blue, respectively.
Semi-catalytic Reaction of 2 and 14b
Complex 2 (9.6 μmol, 8.6 mg) and the internal standard were dissolved in C6D6 (0.8 mL). After the 1H NMR spectrum was recorded, in the glovebox, a solution of 14b (1.2 M in C6D6, 54 μL) was
syringed into the NMR tube. The reaction was monitored at 25 °C by NMR spectroscopy (Figure 5).
By the nearly complete consumption of 14b, intermediate 19b was observed mainly. After that, 19b
ppm (t1)-2.0-1.00.01.02.03.04.05.0
containing 15c (▢) and
(Me3)2CH2 (*) (standard)
▢
▢
*
*
▢
▢
1H
1H1H
1H
1H 1H1H 1H 1H1H
1H 1H1H 1H 1H1H
Page 26
S26
was gradually replaced by 20b. Complexes 19b and 20b were only characterized by NMR analysis
because of their thermal instability.
[(LZr)2(LZrNMe2)(μ-NCH2CMe2CH2C≡CPh)] (19b): 1H NMR (C6D6, 400 MHz): δ 7.46–7.43
(2H, overlap, Ph-H, ortho), 7.02–6.95 (3H, overlap, Ph-H, meta and para), 5.07 (2H, m, NCHHCH2
+ N′CHHCH2), 4.93 (1H, dd, J = 6.6, 12.4 Hz, NCHHCH2), 4.78 (2H, m, N″CH2CH2), 4.47 (1H, dd,
7.2, 12.4 Hz, N′CHHCH2), 2.99–2.88 (1H, overlap, NCH2CHH), 2.85–2.73 (1H, overlap,
NCH2CHH), 2.86–2.65 (2H, overlap, N″CH2CH2), 2.80 (6H, s, NMe2), 2.80–2.67 (1H, overlap,
N′CH2CHH), 2.63–2.51 (1H, overlap, N′CH2CHH), 2.51 (1H, d, J = 12.0 Hz, NCHHCMe2CH2),
2.34 (1H, d, J = 12.4 Hz, NCH2CMe2CHH), 2.26, 2.21, 2.18, 2.18, 2.15, 2.14, 2.09, 2.04, 1.97, 1.96,
1.95, 1.92 (3H × 12, s, C5Me4 × 3), 1.91 (1H, overlap, NCH2CMe2CHH), 1.38 (1H, d, J = 12.0 Hz,
NCHHCMe2CH2) ppm.
Figure S15. Comparison of 1H NMR partial spectra of complexes 5 and 19b (C6D6, 25 °C):
Characteristic NCH2CH2(support) and NMe2 protons are indicated in red and blue, respectively.
[(LZrNMe2)2{LZr(2-benzylidene-4,4-dimethylpyrrolidide)}] (20b): 1H NMR (C6D6, 400 MHz): δ
7.36 (2H, d, J = 4.3 Hz, Ph-H), 7.14 (2H, overlap, Ph-H), 7.02 (1H, overlap, Ph-H), 5.25 (1H, br s,
C=CHPh), 4.83 (1H, m, NCHHCH2), 4.51 (1H, dt-like ddd, J = 5.6, 11.6 Hz, N′CHHCH2), 4.36 (1H,
dd, J = 6.6, 12.8 Hz, N′CHHCH2), 4.29 (1H, br, N″CHHCH2), 4.03 (1H, br, N″CHHCH2), 3.89 (1H,
br, NCHHCH2), 3.27 (1H, d, J = 10.4 Hz, C5HH, pyrrolidide), 3.15 (1H, d, J = 10.4 Hz, C5HH,
pyrrolidide), 2.94–2.80 (1H, overlap, N′CH2CHH), 2.89 (6H, s, NMe2), 2.78–2.68 (2H, overlap,
NCH2CH2), 2.76–2.64 (1H, overlap, N′CH2CHH), 2.74 (6H, s, NMe2), 2.67–2.49 (2H, overlap,
ppm (t1)2.002.503.003.504.004.505.00
*
*
****
1H1H + 1H + 1H + 2H
NMe2 (6H)
1H + 1H 1H 2H 1H
1H + 1H 1H 2H 1H
NMe2 (6H)
containing 14b (*) and 16b (**)
1H1H + 1H + 2H + 1H
Page 27
S27
N″CH2CH2), 2.60 (2H, br, C3H2, pyrrolidide), 2.13, 2.09, 2.08, 2.041, 2.036, 1.99, 1.97, 1.96, 1.95,
1.94, 1.92, 1.89 (3H × 12, s, C5Me4 × 3), 1.13 (3H, s, CMeMe), 1.09 (3H, s, CMeMe) ppm. 13C{1H}
NMR (C6D6, 100 MHz): δ 160.8 (C2, pyrrolidide), 143.0, 128.9, 125.5, 121.2 (Ph), 130.6, 129.0,
126.4, 121.2, 120.8, 120.5, 120.4, 119.3, 119.0, 118.8, 117.6, 116.0, 115.6, 114.3 (C5Me4 × 3), 95.5
(C=CHPh), 66.6 (C5, pyrrolidide), 62.8 (NCH2CH2), 61.5 (N″CH2CH2), 59.3 (N′CH2CH2), 48.6 (C3,
pyrrolidide), 46.3 (NMe2), 46.1 (NMe2), 38.7 (C4, pyrrolidide), 29.6 (N″CH2CH2), 29.4 (N′CH2CH2),
28.9 (NCH2CH2), 28.59 (CMeMe), 28.56 (CMeMe), 13.1, 12.4, 11.9, 11.70, 11.66, 11.66, 11.5, 11.1,
11.0, 10.67, 10.65, 10.3 (C5Me4 × 3) ppm. One Cp-ring carbon resonance of the NCH2CH2C5Me4
fragment is missing, probably, due to signal broadening.
Figure S16. The most plausible structure of 20b: (a) assignment of resonances of the supporting
ligands (green) and their arrangement by HSQC, HMBC, and ROESY (blue arrows), and (b)
arrangement of other ligand fragments by ROESY (blue arrows).
Page 28
S28
Table S1. Crystal, measurement, refinement data for complexes 2, 3a, 4a, 4c, 5, 6b, and 7.
Complex 2 3a 4a
Empirical formula C39H66N6Zr3 C45H81N7Zr3 C42H72N6Zr3
Formula weight 892.63 993.82 934.71
Temperature [K] 123(2) 123(2) 123(2)
Crystal system Orthorhombic Monoclinic Triclinic
Space group Pna21 Cc P-1
a [Å] 22.5649(8) 11.5237(5) 11.4107(5)
b [Å] 10.0550(3) 22.4323(9) 11.8142(7)
c [Å] 18.0848(7) 17.9161(7) 18.1472(8)
α [°] 90 90 83.119(2)
β [°] 90 93.203(2) 81.923(1)
γ [°] 90 90 63.834(2)
V [Å3] 4103.3(2) 4624.1(3) 2169.3 (2)
Z 4 4 2
ρ [Mg m-3] 1.445 1.428 1.431
μ [mm-1] 0.782 0.702 0.743
F(000) 1848 2080 972
Crystal size 0.43 x 0.12 x 0.10 0.22 x 0.05 x 0.04 0.18 x 0.12 x 0.10
θ range [°] 3.161 to 27.482 3.098 to 27.482 3.072 to 27.481
Index ranges -25<=h=<29 -14<=h=<13 -13<=h=<14
-13<=k=<12 -29<=k=<29 -15<=k=<15
-23<=l=<23 -23<=l=<23 -23<=l=<23
Refl. Collected 36849 22594 21699
Indep. Refl. [R(int)] 9387 [0.0784] 22242 [0.0467] 9869 [0.0298]
Abs. correction Empirical Empirical Empirical
Max. and min. transmission 1.0000, 0.1568 1.0000, 0.6975 1.0000, 0.6397
Data / restraints / parameters 9387 / 1 / 470 9758 / 12 / 527 9869 / 9 / 481
GOF on F2 1.012 0.962 1.030
R1 [I>2σ(I)] 0.0459 0.0257 0.0644
wR2 (all data) 0.1091 0.0541 0.1771
Largest diff. peak and hole [eÅ-3] 1.037, -1.182 0.769, -0.547 5.846, -1.143
Page 29
S29
Table S1. (continued)
Complex 4c 5 6b
Empirical formula C45H78N6Zr3 C40H65N5Zr3 C58H71Br3N6Zr3
Formula weight 976.79 889.63 1365.59
Temperature [K] 123(2) 159(2) 123(2)
Crystal system Monoclinic Monoclinic Monoclinic
Space group P21/c P21/n P21/n
a [Å] 21.1636(10) 11.9363(4) 12.2505(5)
b [Å] 12.1570(7) 17.9407(5) 22.8392(9)
c [Å] 18.4466(8) 19.9910(6) 19.9157(7)
α [°] 90 90 90
β [°] 105.387(2) 105.446(1) 96.852(1)
γ [°] 90 90 90
V [Å3] 4575.9(4) 4126.4(2) 5532.4(4)
Z 4 4 4
ρ [Mg m-3] 1.418 1.432 1.640
μ [mm-1] 0.708 0.776 2.765
F(000) 2040 1840 2744
Crystal size 0.28 x 0.10 x 0.05 0.14 x 0.12 x 0.10 0.13 x 0.08 x 0.07
θ range [°] 2.995 to 26.368 3.103 to 27.459 3.067 to 26.371
Index ranges -26<=h=<26 -15<=h=<15 -15<=h=<15
-15<=k=<15 -23<=k=<23 -28<=k=<28
-21<=l=<23 -25<=l=<25 -24<=l=<22
Refl. Collected 65906 40547 47929
Indep. Refl. [R(int)] 9338 [0.0628] 9422 [0.1040] 11297 [0.1454]
Abs. correction Empirical Empirical Numerical
Max. and min. transmission 1.0000, 0.7219 1.0000, 0.6916 0.8154, 0.7379
Data / restraints / parameters 9338 / 0 / 517 9422 / 0 / 445 11297 / 0 / 654
GOF on F2 1.029 1.039 1.030
R1 [I>2σ(I)] 0.0347 0.0549 0.0596
wR2 (all data) 0.0812 0.1097 0.1665
Largest diff. peak and hole [eÅ-3] 0.702, -0.538 0.908, -0.740 0.959, -1.054
Page 30
S30
Table S1. (continued)
Complex 7
Empirical formula C58H89N5O1Zr3
Formula weight 1146.00
Temperature [K] 123(2)
Crystal system Triclinic
Space group P-1
a [Å] 12.8478(8)
b [Å] 13.0149(9)
c [Å] 18.0443(11)
α [°] 112.234(2)
β [°] 101.979(2)
γ [°] 92.165(2)
V [Å3] 2709.4(3)
Z 2
ρ [Mg m-3] 1.405
μ [mm-1] 0.610
F(000) 1200
Crystal size 0.20 x 0.05 x 0.04
θ range [°] 3.124 to 27.477
Index ranges -16<=h=<16
-16<=k=<16
-23<=l=<23
Refl. Collected 27169
Indep. Refl. [R(int)] 12318 [0.0967]
Abs. correction Empirical
Max. and min. transmission 1.0000, 0.5101
Data / restraints / parameters 12318 / 0 / 579
GOF on F2 1.064
R1 [I>2σ(I)] 0.0638
wR2 (all data) 0.1752
Largest diff. peak and hole [eÅ-3] 1.032, -1.113
Page 31
S31
ppm (t1)3.504.004.50
4.7
43
4.7
27
4.7
16
4.7
09
4.7
00
4.6
93
4.6
83
4.6
67
4.6
19
4.6
08
4.6
01
4.5
92
4.5
85
4.5
75
4.5
59
4.2
56
4.2
42
4.2
31
4.2
25
4.2
17
4.2
11
4.2
01
4.1
86
3.9
40
3.9
35
3.9
26
3.9
21
3.9
09
3.9
03
3.8
96
3.8
90
3.6
21
3.6
06
3.5
87
3.5
73
3.4
86
3.4
71
3.4
51
3.4
38
3.4
35
1.0
0
1.0
0
1.0
1
1.0
0
0.9
8
1.0
3
1H NMR (C6D6, 400 MHz)
solvent
ppm (t1)0.01.02.03.04.05.06.07.08.0
2.9
73
2.9
48
2.7
61
1.0
0
1.0
0
1.0
11
.00
0.9
81
.03
12
.34
5.5
35
.57
2.9
35
.67
5.6
32
.92
5.5
02
.60
2.5
42
.51
2.5
3
ppm (t1)1.9001.9502.0002.0502.100
2.1
24
2.1
00
2.0
96
2.0
50
2.0
14
1.9
78
1.9
64
1.9
36
1.9
22
1.9
10
2.9
3
5.6
7
5.6
3
2.9
2
5.5
02
.60
2.5
42
.51
2.5
3
2
Zr NMe2N
Zr
N
NMe2
Zr
N
NMe2
COSY of 2 (C6D6, 400 MHz)
ppm (t2)2.503.003.504.004.50
2.50
3.00
3.50
4.00
4.50
ppm (t1
Page 32
S32
ppm (t1)050100150
130
.35
130
.04
125
.93
120
.87
119
.64
118
.73
118
.62
118
.35
117
.79
116
.55
115
.99
114
.94
114
.20
113
.73
113
.48
60.
68
59.
66
58.
54
46.
70
46.
10
44.
84
29.
54
28.
71
28.
25
12.
94
11.
74
11.
60
11.
57
11.
10
10.
94
10.
80
10.
73
10.
68
10.
63
10.
55
ppm (t1)9.010.011.012.013.0
12
.94
11
.74
11
.60
11
.57
11
.10
10
.94
10
.80
10
.73
10
.68
10
.63
10
.55
13C NMR (C6D6, 100 MHz)
2
Zr NMe2N
Zr
N
NMe2
Zr
N
NMe2
solvent
ppm (t2)3.003.504.00
125.0
126.0
127.0
128.0
129.0
130.0
131.0
132.0
ppm (t1
ppm (t2)2.7002.7502.8002.8502.9002.9503.000
43.0
44.0
45.0
46.0
47.0
48.0
49.0ppm (t1
ppm (t2)3.504.004.50
57.0
58.0
59.0
60.0
61.0
62.0
ppm (t1
ppm (t2)1.9001.9502.0002.0502.1002.150
115.0
120.0
ppm (t1
HMQC of 2 (C6D6, 400 MHz) HMBC of 2 (C6D6, 400 MHz)
Page 33
S33
1H NMR (C6D6, 400 MHz)
ppm (t1)0.01.02.03.04.05.06.07.08.0
1.9
50
.82
2.2
3
0.8
11
.00
0.8
4
6.5
9
1.1
7
1.0
5
14
.18
1.2
42
.84
30
.74
5.8
62
.71
2.5
32
.70
4.9
81
.00
12
.61
7.2
56
.00
2.0
3
19
.48
11
.48
ppm (t1)0.501.00
1.2
80
1.2
63
1.2
45
1.2
27
1.2
09
1.1
90
1.0
74
1.0
55
1.0
37
1.0
28
1.0
09
0.9
91
0.9
65
0.9
48
0.9
30
0.9
12
0.7
97
0.7
78
0.7
60
0.3
85
0.3
73
0.3
65
0.3
50
12
.61
7.2
5
6.0
0
19
.48
11
.48
Zr NH
Zr
N Zr
NH
NH
NH
NH
N
3a
solvent
standard (□)n-PrNH2 (▲)
1H NMR of 3a (C6D6, 400 MHz)
ppm (t1)2.503.003.504.004.50
4.5
23
4.4
99
4.4
82
4.4
05
4.3
93
4.3
76
4.3
64
4.1
16
4.0
85
4.0
58
3.9
93
3.9
78
3.9
61
3.9
46
3.9
29
3.9
14
3.8
56
3.8
41
3.8
25
3.8
11
3.7
94
3.7
79
3.6
09
3.5
93
3.5
79
3.4
84
3.4
66
3.4
33
3.3
41
3.3
23
3.3
10
3.2
91
3.2
77
2.8
53
2.8
36
2.5
96
2.5
74
2.3
58
2.3
46
2.3
25
2.3
12
1.9
5
0.8
2
2.2
1
0.8
1
1.0
0
0.8
4
6.5
9
1.1
7
14
.1
1.2
4
2.0
3
ppm (t1)1.9001.9502.0002.0502.1002.1502.2002.250
2.2
70
2.2
01
2.1
88
2.1
86
2.1
74
2.1
53
2.1
43
2.0
11
1.9
45
1.9
07
1.8
82
2.8
4
5.8
6
2.7
1
2.5
3
2.7
0
32
.76
Me2NH
Page 34
S34
COSY of 3a (C6D6, 400 MHz)
ppm (t2)0.501.001.502.002.503.003.504.004.50
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50ppm (t1
Page 35
S35
ppm (t1)050100150
12
9.5
3
12
2.1
91
22
.02
11
8.1
81
17
.87
11
7.4
71
17
.41
11
6.5
31
16
.34
11
6.0
2
11
5.1
01
14
.86
11
4.3
5
11
3.7
1
62
.99
60
.01
59
.68
55
.82
55
.62
54
.62
54
.38
31
.42
31
.24
30
.60
30
.34
29
.98
29
.41
28
.82
13
.27
13
.11
12
.98
12
.82
12
.56
12
.32
12
.23
12
.14
12
.00
11
.75
11
.49
11
44
10
51
13C NMR (C6D6, 100 MHz)
ppm (t1)29.0029.5030.0030.5031.0031.50
31
.42
31
.24
30
.60
30
.34
29
.98
29
.41
28
.82
Zr NH
Zr
N Zr
NH
NH
NH
NH
N
3a
solvent
standard (□)n-PrNH2 (▲)
Me2NH
ppm (t1)114.0115.0116.0117.0118.0119.0120.0121.0122.0
12
2.1
9
12
2.0
2
11
8.1
8
11
7.8
7
11
7.4
7
11
7.4
1
11
6.5
31
16
.34
11
6.0
2
11
5.1
0
11
4.8
6
11
4.3
5
11
3.7
1
ppm (t1)10.5011.0011.5012.0012.5013.00
13.
27
13.
11
12.
98
12.
82
12.
56
12.
32
12.
23
12.
14
12.
00
11.
75
11.
49
11.
44
11.
37
11.
33
11.
28
10.
51
13C NMR of 3a (C6D6, 100 MHz)
Page 36
S36
ppm (t1)0.01.02.03.04.05.06.07.08.0
1.0
01
.04
2.1
2
1.0
4
0.9
30
.91
5.4
9
1.1
11
.06
1.1
72
.11
1.3
21
.06
19
.16
2.9
1
0.9
71
.15
7.9
4
5.7
56
.07
2.4
92
.97
3.0
16
.09
ppm (t1)0.9000.9501.0001.0501.100
1.1
08
1.1
05
1.0
91
1.0
88
1.0
28
1.0
18
1.0
11
1.0
02
0.9
63
0.9
46
0.9
19
0.9
02
5.7
5
6.0
7
2.4
9
2.9
7
ppm (t1)4.504.604.704.804.905.005.10
5.0
08
4.9
90
4.9
79
4.9
61
4.8
98
4.8
81
4.8
70
4.8
53
4.8
42
4.8
25
4.5
68
4.5
57
4.5
27
4.5
17
1.0
0
1.0
4
2.1
2
1H NMR (C6D6, 400 MHz)
Zr NH
Zr
N Zr
N
NH
N
NH
4c
solvent
ppm (t1)2.503.003.50
3.7
60
3.7
46
3.7
27
3.7
13
3.6
91
3.6
72
3.6
53
3.5
21
3.5
01
3.4
84
3.4
22
3.4
10
3.3
89
3.3
77
3.3
41
3.3
20
3.2
75
3.1
69
3.1
51
3.1
34
3.1
20
3.1
02
3.0
61
3.0
47
3.0
31
3.0
14
3.0
00
2.5
75
2.5
54
2.5
40
2.5
23
2.5
08
2.4
91
2.4
76
2.4
63
1.0
4
0.9
3
0.9
1
5.4
9
1.1
1
1.0
6
1.1
7
2.1
1
1.3
2
1.0
6
ppm (t1)1.701.801.902.002.102.202.30
2.2
65
2.1
97
2.1
83
2.1
70
2.1
27
2.1
20
2.0
72
2.0
64
2.0
29
1.9
29
1.8
15
1.6
88
19
.16
2.9
1
7.9
4
3.0
1
6.0
9
ppm (t1)1.3501.4001.4501.5001.550
1.5
72
1.5
56
1.5
39
1.5
23
1.5
07
1.4
91
1.4
75
1.4
23
1.4
08
1.3
90
1.3
74
0.9
7
1.1
5
1H NMR of 4c (C6D6, 400 MHz)
Page 37
S37
ppm (f2)2.503.003.504.004.505.00
2.50
3.00
3.50
4.00
4.50
5.00ppm (f1)
COSY of 4c (C6D6, 400 MHz)
Page 38
S38
ppm (t1)050100150
13
3.7
1
12
5.2
4
12
4.1
6
11
9.5
11
19
.41
11
7.8
6
11
7.0
3
11
6.4
21
16
.36
11
5.5
7
11
5.0
41
14
.91
11
4.6
8
11
4.0
0
11
2.8
2
72
.05
66
.48
65
.73
60
.57
59
.34
55
.92
34
.31
34
.15
33
.83
32
.13
29
.35
29
.09
21
.54
21
.10
20
.97
20
.84
12
.09
12
.00
11
.83
11
.75
11
.74
11
.68
11
.60
11
.45
11
22
10
88
10
46
ppm (t1)112.0113.0114.0115.0116.0117.0118.0119.0
11
9.5
1
11
9.4
11
17
.86
11
7.0
3
11
6.4
21
16
.36
11
5.5
7
11
5.0
4
11
4.9
1
11
4.6
81
14
.00
11
2.8
2
Zr NH
Zr
N Zr
N
NH
N
NH
4c
13C NMR (C6D6, 100 MHz)solvent
ppm (t1)28.029.030.031.032.033.034.035.0
34
.31
34
.15
33
.83
32
.13
29
.35
29
.09
ppm (t1)21.0021.50
21.
54
21.
10
20.
97
20.
84
ppm (t1)10.5011.0011.5012.00
12.
09
12.
00
11.
83
11.
75
11.
74
11.
68
11.
60
11.
45
11.
22
10.
93
10.
88
10.
46
13C NMR of 4c (C6D6, 100 MHz)
Page 39
S39
HMBC of 4c (C6D6)
ppm (f2)1.701.801.902.002.102.202.30
115.0
120.0
125.0
130.0
135.0
ppm (f1
ppm (f2)1.001.502.002.503.003.50
55.0
60.0
65.0
70.0
ppm (f1
ppm (f2)0.9000.9501.0001.0501.1001.150
32.50
33.00
33.50
34.00
34.50
35.00
35.50
36.00ppm (f1
Page 40
S40
ppm (t1)0.01.02.03.04.05.06.07.08.0
1.5
20
1.4
90
0.8
54
1.0
0
1.0
32
.09
2.0
4
1.0
31
0.1
9
1.0
5
6.1
12
.89
2.8
92
.87
3.3
52
.71
2.7
15
.65
5.6
3
0.9
8
8.5
2
ppm (t1)2.402.502.602.702.802.903.00
2.9
51
2.9
33
2.9
22
2.8
14
2.7
77
2.7
08
2.6
89
2.4
59
2.4
54
2.4
39
1.0
3
10
.19
1.0
5
Zr N
Zr
N Zr
N
NMe2
N
5
1H NMR (C6D6, 400 MHz)
solvent
ppm (t1)4.404.504.604.704.804.905.005.10
5.0
79
4.9
62
4.9
46
4.9
31
4.9
14
4.7
97
4.4
24
4.4
06
4.3
92
4.3
74
1.0
0
1.0
3
2.0
9
2.0
4
ppm (t1)1.9001.9502.0002.0502.1002.1502.200
2.2
35
2.2
28
2.1
94
2.1
74
2.1
57
2.1
00
2.0
27
2.0
19
1.9
81
1.9
20
1.9
10
1.8
74
6.1
1
2.8
9
2.8
9
2.8
7
3.3
5
2.7
1
2.7
1
5.6
5
5.6
3
1H NMR of 5 (C6D6, 400 MHz)
Page 41
S41
COSY of 5 (C6D6, 400 MHz)
ppm (f2)1.502.002.503.003.504.004.505.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
5.00ppm (f1
Page 42
S42
ppm (t1)050100150
13
2.4
01
13
0.1
69
12
8.8
31
12
2.6
49
12
1.2
38
12
0.8
31
11
9.7
66
11
8.9
32
11
6.3
37
11
5.2
69
11
4.8
96
11
4.0
11
11
3.8
60
11
3.4
17
70
.495
67
.739
63
.660
62
.428
45
.158
33
.816
31
.155
30
.072
29
.398
28
.311
12
.677
12
.286
11
.847
11
.654
11
.312
11
.266
11
.156
11
.132
10
.969
10
.894
10
.879
10
.528
ppm (t1)
9.5010.0010.5011.0011.5012.0012.5013.00
12.
67
7
12.
28
6
11.
84
71
1.6
54
11.
31
21
1.2
66
11.
15
61
1.1
32
10.
96
9
10.
89
41
0.8
79
10.
52
8
13C NMR (C6D6, 100 MHz)
Zr N
Zr
N Zr
N
NMe2
N
5
solvent
ppm (t1)10.5011.0011.5012.0012.50
12
.67
7
12
.28
6
11
.84
7
11
.65
4
11
.31
21
1.2
66
11
.15
61
1.1
32
10
.96
9
10
.89
4
10
.87
9
10
.52
8
13C NMR of 5 (C6D6, 100 MHz)
Page 43
S43
ppm (f2)4.404.504.604.704.804.905.005.10
65.0
70.0
ppm (f1
ppm (f2)1.502.00
60.0
61.0
62.0
63.0
64.0
65.0
66.0ppm (f1
ppm (f2)2.402.502.602.702.802.903.00
65.0
70.0
ppm (f1
HMQC of 5 (C6D6) HMBC of 5 (C6D6)
ppm (f2)1.902.002.102.202.30
115.0
120.0
125.0
130.0
ppm (f1
Page 44
S44
ppm (f1)0.05.0
1.0
1
2.0
0
0.9
22
.97
2.0
40
.97
2.0
20
.92
2.0
3
1.0
1
1.0
0
1.0
2
0.9
20
.80
2.9
9
2.9
32
.66
3.1
30
.75
2.9
22
.95
6.5
55
.89
0.6
62
.92
1.7
72
.87
0.5
7
0.9
8
ppm (f1)0.05.0
1.0
1
2.0
0
0.9
22
.97
2.0
40
.97
2.0
20
.92
2.0
3
1.0
1
1.0
0
1.0
2
0.9
20
.80
2.9
9
2.9
32
.66
3.1
30
.75
2.9
22
.95
6.5
55
.89
0.6
62
.92
1.7
72
.87
0.5
7
0.9
8
ppm (f1)0.4500.5000.550
0.5
36
0.5
12
0.4
83
0.9
8
ppm (f1)6.507.007.50
7.4
82
7.4
64
7.3
65
7.3
44
6.9
94
6.9
74
6.8
29
6.8
13
6.4
55
6.4
34
6.2
77
6.2
57
6.1
95
6.1
73
0.9
2
2.9
7
2.0
4
0.9
7
2.0
2
0.9
2
2.0
3
1H NMR (C6D6, 400 MHz)
solvent
pentane
ppm (f1)2.503.003.504.004.505.00
5.1
83
5.1
64
5.1
45
5.1
26
5.1
03
4.4
70
4.4
50
4.4
39
4.4
14
4.0
08
3.9
92
3.9
82
3.9
66
3.3
75
3.3
57
3.3
39
3.3
22
3.3
03
2.8
14
2.7
99
2.7
79
2.7
64
2.7
28
2.7
07
2.6
86
2.5
87
2.5
74
2.5
69
2.5
40
1.0
1
2.0
0
1.0
1
1.0
0
1.0
2
0.9
2
0.8
0
ppm (f1)1.401.501.601.701.801.902.002.102.202.30
2.2
81
2.2
14
2.1
58
2.0
87
1.9
47
1.8
35
1.7
88
1.7
27
1.7
18
1.6
82
1.6
21
1.5
79
1.5
09
1.3
97
2.9
9
2.9
3
2.6
6
3.1
3
0.7
5
2.9
2
2.9
5
6.5
5
5.8
9
0.6
6
2.9
2
1.7
7
2.8
7
1H NMR of 6b (C6D6, 400 MHz)
toluene
Page 45
S45
ppm (f2)6.507.007.50
6.50
7.00
7.50
ppm (f1
ppm (f2)2.002.503.003.504.004.505.00
2.00
2.50
3.00
3.50
4.00
4.50
5.00
ppm (f1
ppm (f2)0.501.001.50
0.50
1.00
1.50
ppm (f1
COSY of 6b (C6D6, 400 MHz)
ppm (f1)050100150
15
9.2
2
15
8.0
81
54
.68
13
5.1
41
31
.66
13
1.4
61
31
.06
13
0.9
3
12
6.1
51
26
.06
12
5.9
8
12
3.1
3
12
2.1
31
21
.92
12
0.7
71
20
.64
12
0.4
51
20
.21
11
9.6
3
11
8.7
91
18
.77
11
7.8
61
16
.01
11
5.8
11
13
.83
11
2.0
91
10
.19
11
0.1
41
06
.94
71
.55
51
.35
44
.42
30
.11
28
.25
23
.88
14
.42
13
.26
12
.43
12
.03
11
.81
11
.70
11
.50
10
.94
10
.84
10
.76
9.9
89
.82
13C{1H} NMR (C6D6, 400 MHz)solvent
Zr N
Zr
N Zr
N
N
NH
Br
Br
Br
NH2
6b
Page 46
S46
ppm (f2)6.507.007.50
120.0
125.0
130.0
ppm (f1
ppm (f2)1.401.501.601.701.801.902.002.102.202.30
9.0
10.0
11.0
12.0
13.0
14.0
15.0ppm (f1
ppm (f2)2.03.04.05.0
45.0
50.0
55.0
60.0
65.0
70.0
75.0ppm (f1
ppm (f2)0.501.001.502.002.503.00
24.0
25.0
26.0
27.0
28.0
29.0
30.0
31.0ppm (f1
HSQC of 6b (C6D6)
HMBC of 6b (C6D6)
ppm (f2)5.506.006.507.007.50
110
120
130
140
150
160ppm (f1
ppm (f2)2.503.003.504.004.50
120.0
125.0
130.0
135.0
ppm (f1
ppm (f2)1.401.501.601.701.801.902.002.102.202.30
115.0
120.0
125.0
130.0
135.0
ppm (f1
ppm (f2)1.502.002.503.00
45.0
50.0
55.0
60.0
65.0
70.0
ppm (f1
Page 47
S47
1H NMR (C6D6, 400 MHz)
ppm (t1)0.05.0
3.0
67
2.6
80
1.6
36
1.5
30
0.9
91
.00
1.9
7
0.9
7
2.9
9
5.7
80
.98
1.0
87
.32
1.7
11
.04
8.8
68
.62
3.0
93
.21
3.0
86
.00
8.7
88
.86
1.0
5
3.0
4
ppm (t1)6.806.907.007.107.207.307.40
7.3
38
7.3
33
7.3
18
7.3
13
7.2
78
7.2
74
7.2
59
7.2
55
6.8
32
6.8
13
6.7
93
0.9
9
1.0
0
1.0
5
solvent
ppm (t1)4.404.504.604.704.804.905.005.10
5.0
65
5.0
51
5.0
35
5.0
20
5.0
04
4.9
91
4.9
61
4.9
47
4.9
31
4.9
24
4.9
19
4.9
03
4.8
93
4.8
72
4.6
96
4.6
78
4.6
66
4.6
48
4.6
32
4.6
22
4.6
12
4.6
01
4.5
92
4.5
81
4.4
36
4.4
17
4.4
04
4.3
86
1.9
7
0.9
7
2.9
9
ppm (t1)1.801.902.002.102.202.30
2.3
11
2.2
59
2.2
41
2.0
49
1.9
72
1.9
68
1.9
41
1.9
31
1.8
65
1.8
08
3.0
9
3.2
1
3.0
8
6.0
0
8.7
8
8.8
6
3.0
4
1H NMR of 7 (C6D6, 400 MHz)
Page 48
S48
ppm (f2)2.503.003.504.004.505.00
2.50
3.00
3.50
4.00
4.50
5.00
ppm (f1
COSY of 7 (C6D6, 400 MHz)
ppm (t1)050100150
16
3.1
1
13
8.1
9
13
6.8
9
13
0.0
4
12
8.5
6
12
5.5
3
12
5.0
6
12
4.3
8
12
2.0
5
12
1.6
21
21
.34
11
9.6
01
19
.45
11
7.8
2
11
6.3
41
16
.16
11
5.6
71
15
.28
67
.33
66
.96
61
.03
50
.26
49
.60
37
.13
35
.81
35
.78
32
.39
29
.82
29
.66
29
.39
14
.29
13
.77
12
.91
12
.68
12
.22
11
.98
11
.89
11
.73
11
.55
11
.20
10
.54
10
.00
13C NMR (C6D6, 100 MHz)solvent
Page 49
S49
ppm (t2)1.801.902.002.102.202.30
115.0
120.0
125.0
130.0
ppm (t1
ppm (t2)2.502.602.702.802.903.003.103.203.30
48.00
48.50
49.00
49.50
50.00
50.50
51.00
51.50
ppm (t1
ppm (t2)1.5001.5501.6001.6501.700
135.50
136.00
136.50
137.00
137.50
138.00
138.50
139.00
139.50ppm (t1
ppm (t2)1.5001.5501.6001.650
32.0
33.0
34.0
35.0
36.0
37.0
38.0
ppm (t1
HMBC of 7 (C6D6)
Page 50
S50
ppm (f1)0.01.02.03.04.05.06.07.08.0
2.1
50
1.9
71
1.4
24
0.9
04
0.6
42
1.8
8
2.1
02
.09
6.1
55
.89
9.0
0
17
.80
5.9
3
ppm (f1)3.103.203.303.40
3.4
15
3.3
96
3.3
78
3.2
26
3.2
02
3.1
95
3.1
71
3.1
04
3.0
85
3.0
73
3.0
54
1.8
8
2.1
0
2.0
9
1H NMR (C6D6, 400 MHz)
solvent
ppm (f1)050100150
12
7.5
1
12
4.6
8
10
0.2
7
62
.23
54
.77
35
.15
33
.60
27
.47
13
.94
11
.35
7.7
0
solvent
13C NMR (C6D6, 100 MHz)
Si
NZr
HN
NH
10
Page 51
S51
ppm (t1)0.05.0
4.9
27
4.8
69
4.5
22
4.4
46
3.3
12
3.2
78
2.8
05
2.7
92
2.7
87
2.7
73
1.1
62
1.1
45
1.1
27
0.9
19
0.9
01
0.8
83
1.0
0
1.9
3
0.8
6
0.9
6
5.0
4
2.7
1
0.9
3
0.9
00
.99
3.1
0
2.8
1
2.7
52
.93
3.0
13
.20
2.9
65
.86
2.7
52
.89
3.0
62
.91
ppm (t1)1.801.902.002.102.202.302.40
2.4
44
2.3
29
2.2
63
2.2
22
2.1
84
2.1
29
2.0
30
1.9
45
1.9
27
1.8
17
1.7
97
2.7
1
2.7
5
2.9
33
.01
3.2
02
.96
5.8
6
2.7
52
.89
3.0
62
.91
ppm (t1)-2.200
-2.1
75
-2.1
85
-2.2
10
-2.2
18
0.9
3
ppm (t1)5.3505.4005.450
5.4
14
5.3
94
5.3
82
5.3
64
1.0
0
12a(+ 12a)
N
Zr NH
Zr
N Zr
N
NH
solvent
1H NMR (C6D6, 400 MHz)
ppm (f2)-2.0-1.00.01.02.03.04.05.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
ppm (f1
COSY of 12a (C6D6, 400 MHz)
Page 52
S52
ppm (t1)050100150
13
2.2
21
30
.43
11
9.0
41
18
.90
11
8.5
61
18
.36
11
6.7
11
16
.29
11
4.8
31
14
.72
11
4.2
81
14
.21
11
4.1
31
13
.86
91
.23
72
.13
65
.09
55
.62
52
.64
38
.60
32
.48
31
.35
30
.70
30
.28
19
.53
ppm (t1)9.010.011.012.013.0
13
.02
12
.52
12
.06
11
.65
11
.56
11
.14
10
.97
10
.88
10
.76
10
.44
10
.40
9.9
9
12a(+ 12a)
N
Zr NH
Zr
N Zr
N
NH
solvent
13C NMR (C6D6, 100 MHz)
ppm (f2)2.503.003.504.004.505.005.50
55.0
60.0
65.0
70.0
ppm (f1
ppm (f2)2.0002.0502.1002.1502.2002.2502.300
89.50
90.00
90.50
91.00
91.50
92.00
92.50
93.00
ppm (f1
HSQC of 12a (C6D6) HMBC of 12a (C6D6)
ppm (t2)0.800.901.001.101.20
30
40
50
60
70
80
90
ppm (t1
ppm (t2)2.002.50
115.0
120.0
125.0
130.0
ppm (t1
Page 53
S53
ppm (f1)0.01.02.03.04.05.06.07.08.0
2.7
87
2.7
70
2.7
53
2.2
08
2.1
91
2.1
73
1.6
19
1.6
02
1.5
85
1.5
68
1.5
50
1.1
71
1.9
6
2.0
0
2.0
0
11
.37
solvent
1H NMR (CDCl3, 400 MHz)
ppm (f1)050100150
89
.43
77
.69
41
.30
32
.88
31
.34
27
.31
16
.13
solvent
13C NMR (CDCl3, 100 MHz)
Page 54
S54
1H NMR (CDCl3, 400 MHz)
ppm (f1)0.01.02.03.04.05.06.07.08.0
2.5
26
1.1
28
1.1
10
1.0
91
0.9
08
5.9
9
3.0
2
2.0
01
.89
1.9
4
ppm (f1)2.0502.1002.1502.200
2.1
89
2.1
83
2.1
76
2.1
70
2.1
64
2.1
58
2.1
51
2.1
45
2.1
39
2.1
33
2.1
27
2.1
21
2.0
45
2.0
39
2.0
33
2.0
0
1.8
9
solvent
Page 55
S55
N
Bu-t
15c
ppm (f1)0.01.02.03.04.05.06.07.08.0
1.0
13
1.9
0
2.0
02
.05
8.9
4
2.1
2
ppm (f1)3.7003.7503.800
3.7
94
3.7
90
3.7
86
3.7
82
3.7
78
3.7
71
3.7
68
3.7
65
3.7
58
3.7
54
3.7
50
3.7
46
3.7
42
1.9
0
ppm (f1)1.450
1.4
80
1.4
62
1.4
40
1.4
23
1.4
03
2.1
2
ppm (f1)2.0502.1002.150
2.1
45
2.0
94
2.0
87
2.0
83
2.0
68
2.0
51
2.0
47
2.0
42
2.0
0
2.0
5
standard (□)13c (▲)
solvent
1H NMR (C6D6, 400 MHz)
solvent
13C NMR (C6D6, 100 MHz)
N
Bu-t
15c
standard (□)13c (▲)
ppm (t1)050100150
17
4.9
3
61
.55
46
.94
40
.15
31
.29
30
.17
23
.07
Page 56
S56
ppm (f1)0.05.0
1.9
25
2.0
0
2.0
42
.04
2.0
1
8.8
5
ppm (f1)0.8700.8800.8900.900
0.9
05
0.8
86
0.8
74
0.8
68
8.8
5
ppm (f1)1.5501.600
1.6
29
1.6
11
1.5
92
1.5
74
1.5
55
1.5
37
2.0
1
ppm (f1)2.0902.1002.1102.1202.1302.140
2.1
33
2.1
15
2.0
96
2.0
4
ppm (f1)3.550
3.5
58
3.5
54
3.5
50
3.5
46
3.5
42
2.0
0
standard (□)
solvent
1H NMR (C6D6, 400 MHz)
solvent
13C NMR (C6D6, 100 MHz)
standard (□)
ppm (f1)050100150
17
5.7
7
74
.78
52
.38
38
.28
36
.34
28
.02
19
.90
14
.21
Page 57
S57
ppm (t1)0.01.02.03.04.05.06.07.08.0
1.1
60
.89
0.9
10
.95
1.8
91
.00
5.3
22
.16
1.9
2
1.8
5
6.1
8
1.1
00
.99
1.1
5
7.8
08
.51
17
.65
3.0
53
.07
3.2
02
.98
6.7
02
.63
4.5
42
0.5
32
.99
2.9
95
.08
2.7
5
ppm (t1)0.300.400.500.600.700.80
0.8
72
0.7
55
0.7
39
0.7
23
0.7
08
0.3
40
0.3
21
0.3
06
1.1
0
0.9
9
1.1
5
ppm (t1)1.2801.2901.3001.310
1.3
12
1.3
04
1.2
86
1.2
82
7.8
0
8.5
1
17
.65
1H NMR (C6D6, 400 MHz)
solvent
13c (□)standard (▲)
Zr NH
Zr
N Zr
NH
NH
NH
NH
N
Bu-t
Bu-t
t-Bu
t-Bu
17c
ppm (t1)3.003.504.004.50
4.4
73
4.4
58
4.4
42
4.4
27
4.3
86
4.3
67
4.3
46
4.2
69
4.2
58
4.2
39
4.2
28
4.1
09
4.0
78
4.0
47
3.9
89
3.9
72
3.9
57
3.9
41
3.9
25
3.9
12
3.8
06
3.5
56
3.3
74
2.9
33
1.1
6
0.8
9
0.9
1
0.9
5
1.8
9
1.0
0
5.3
2
2.1
6
1.9
2
ppm (t1)1.902.002.102.202.30
2.2
86
2.2
28
2.2
02
2.1
64
2.1
51
2.1
40
2.1
02
2.0
52
1.9
62
1.9
08
1.8
71
3.0
5
3.0
7
3.2
0
2.9
8
6.7
0
4.5
4
20
.53
2.9
9
2.9
9
5.0
8
2.7
5
1H NMR of 17c (C6D6, 400 MHz)
Page 58
S58
ppm (t2)0.501.001.502.002.503.003.504.004.50
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50ppm (t1
COSY of 17c (C6D6, 400 MHz)
Page 59
S59
13C NMR (C6D6, 100 MHz)
ppm (t1)050100150
12
9.6
8
12
8.7
5
12
2.4
41
22
.17
11
8.4
61
18
.12
11
7.7
41
17
.69
11
6.7
11
16
.44
11
6.1
6
11
5.4
01
14
.95
11
4.4
9
11
3.8
38
9.4
58
9.0
48
8.8
48
8.7
8
79
.62
79
.24
78
.88
77
.95
63
.08
60
.16
57
.50
55
.70
53
.02
51
.81
51
.25
36
.40
36
.37
36
.27
35
.75
31
.83
31
.81
31
.79
31
.71
31
.38
31
.18
28
.74
27
.72
27
.63
18
.74
18
.02
17
.15
17
.07
13
.25
13
.22
12
45
12
03
12
00
11
88
11
71
11
57
solvent
13c (□)standard (▲)
ppm (t1)115.0120.0
12
2.4
4
12
2.1
7
11
8.4
6
11
8.1
2
11
7.7
4
11
7.6
9
11
6.7
1
11
6.4
4
11
6.1
6
11
5.4
0
11
4.9
5
11
4.4
9
11
3.8
3
ppm (t1)11.012.013.014.015.016.017.018.019.0
18
.74
18
.02
17
.15
17
.07
13
.25
13
.22
12
.45
12
.03
12
.00
11
.88
11
.71
11
.57
11
.39
11
.29
10
.85
13C NMR of 17c (C6D6, 100 MHz)
Page 60
S60
ppm (t1)0.05.0
1.2
81
1.2
71
0.9
8
0.9
61
.28
1.0
2
1.0
9
0.8
8
4.3
3
4.1
53
2.8
2
1.1
11
.05
1.0
0
7.0
03
6.1
8
2.9
92
.53
2.2
42
.76
5.1
1
ppm (t1)-2.250-2.200-2.150
-2.1
89
-2.2
14
1.0
0
ppm (t1)0.300.400.500.60
0.5
89
0.5
67
0.3
85
0.3
63
1.1
1
1.0
5
1H NMR (C6D6, 400 MHz)
solvent
ppm (t1)3.003.504.004.505.005.50
5.3
67
5.3
47
5.3
35
5.3
15
4.9
51
4.9
36
4.9
20
4.9
03
4.8
90
4.8
59
4.8
41
4.8
31
4.8
15
4.8
00
4.7
84
4.4
38
4.4
19
4.4
02
4.3
87
4.3
68
3.2
93
3.2
73
3.2
67
3.2
60
3.2
47
3.2
39
3.2
34
3.2
14
3.0
08
2.9
89
2.7
65
0.9
8
0.9
6
1.2
8
1.0
2
1.0
9
0.8
8
4.3
3
ppm (t1)1.801.902.002.102.202.302.402.50
2.4
18
2.2
69
2.2
56
2.2
26
2.2
17
2.0
99
2.0
25
1.9
42
1.9
03
1.8
48
1.8
14
7.0
0
36
.18
2.9
9
2.5
3
2.2
4
2.7
6
5.1
1
1H NMR of 18c (C6D6, 400 MHz)
Page 61
S61
ppm (t1)050100150
13
2.1
8
13
0.6
1
12
6.6
7
89
.30
89
.02
87
.86
79
.89
79
.05
72
.30
65
.14
52
.66
45
.32
39
.10
31
.77
31
.73
27
.71
27
.69
17
.55
13C NMR (C6D6, 100 MHz)solvent
ppm (t1)114.0115.0116.0117.0118.0119.0
11
9.2
9
11
9.1
1
11
8.7
9
11
8.5
0
11
6.9
0
11
6.4
2
11
5.1
0
11
4.9
7
11
4.4
8
11
4.3
41
14
.30
11
4.1
5
ppm (t1)10.0010.5011.0011.5012.0012.5013.00
13
.03
12
.03
11
.58
11
.47
11
.40
11
.09
11
.08
11
.02
10
.98
10
.90
10
.45
10
.00
13C NMR of 18c (C6D6, 100 MHz)
Page 62
S62
ppm (f2)2.002.503.003.504.004.505.005.50
50.0
55.0
60.0
65.0
70.0
75.0
ppm (f1
ppm (f2)1.902.002.102.202.302.402.50
85.50
86.00
86.50
87.00
87.50
88.00
88.50
ppm (f1
ppm (f2)2.002.503.003.504.004.505.00
126.0
127.0
128.0
129.0
130.0
131.0
132.0
133.0
ppm (f1
ppm (f2)1.801.902.002.102.202.302.40
114.0
115.0
116.0
117.0
118.0
119.0
120.0ppm (f1
HSQC of 18c (C6D6) HMBC of 18c (C6D6)
Page 63
S63
1H NMR (C6D6, 400 MHz)
ppm (t1)0.05.0
2.8
92
2.7
37
4.0
9
5.2
03
.05
1.0
00
.98
0.8
70
.92
0.8
5
1.0
0
0.9
51
.67
5.7
3
2.7
42
.91
2.6
72
.84
2.5
52
.94
3.0
72
.64
2.7
45
.50
2.5
82
.57
2.6
3
4.2
2
6.7
3
ppm (t1)1.100
1.1
30
1.0
86
2.7
4
2.9
1
ppm (t1)3.1003.1503.2003.2503.300
3.2
83
3.2
56
3.1
64
3.1
37
1.0
0
0.9
8
complex 2 (□)16b (▲)
solvent
ppm (t1)4.004.505.00
5.2
54
4.8
72
4.8
53
4.8
48
4.8
40
4.8
30
4.8
18
4.7
97
4.5
48
4.5
34
4.5
17
4.5
03
4.4
88
4.4
74
4.3
84
4.3
68
4.3
53
4.3
36
4.2
90
4.0
27
3.8
92
0.8
7
0.9
2
0.8
5
1.0
0
0.9
5
1.6
7
ppm (t1)1.9001.9502.0002.0502.1002.150
2.1
34
2.0
91
2.0
78
2.0
42
2.0
37
1.9
89
1.9
72
1.9
59
1.9
50
1.9
36
1.9
18
1.8
87
2.6
7
2.8
4
2.5
5
2.9
4
3.0
7
2.6
4
2.7
4
5.5
0
2.5
8
2.5
7
2.6
3
1H NMR of 20b (C6D6, 400 MHz)
Page 64
S64
ppm (t2)2.503.003.504.004.505.00
2.50
3.00
3.50
4.00
4.50
5.00
ppm (t1
COSY of 20b (C6D6, 400 MHz)
Page 65
S65
13C NMR (C6D6, 100 MHz)
ppm (t1)050100150
16
0.7
7
14
2.9
7
13
0.5
6
12
9.0
41
28
.93
12
6.4
4
12
5.5
4
12
1.1
71
20
.77
12
0.5
21
20
.36
11
9.3
21
19
.00
11
8.7
6
11
7.6
01
15
.98
11
5.6
3
11
4.3
1
95
.53
66
.58
62
.81
61
.51
59
.25
48
.65
46
.30
46
.09
38
.74
29
.57
29
.40
28
.88
28
.60
28
.57
13
.06
12
.43
11
.92
11
.70
11
.66
11
.48
11
.14
11
.01
10
.68
10
.66
10
32
solvent
ppm (t1)115.0120.0125.0
12
6.4
4
12
5.5
4
12
1.1
7
12
0.7
7
12
0.5
2
12
0.3
6
11
9.3
2
11
9.0
01
18
.76
11
7.6
0
11
5.9
8
11
5.6
3
11
4.3
1
ppm (t1)10.5011.0011.5012.0012.5013.00
13
.06
12
.43
11
.92
11
.70
11
.66
11
.48
11
.14
11
.01
10
.68
10
.66
10
.32
13C NMR of 20b (C6D6, 100 MHz)
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ppm (t2)4.004.505.00
60.0
65.0
70.0
75.0
80.0
85.0
90.0
95.0
ppm (t1
ppm (t2)2.602.702.802.903.003.103.203.30
45.0
50.0
55.0
60.0
65.0
ppm (t1
ppm (t2)2.602.702.802.903.003.103.203.30
155.0
160.0
165.0
ppm (t1
ppm (t2)1.001.502.002.50
30
40
50
60
70ppm (t1
HSQC of 20b (C6D6) HMBC of 20b (C6D6)