4/6/2015 1 Transition Metals in Coordination Chemistry IA VIIIA 1 H 1.008 IIA IIIA IVA VA VIA VIIA 2 He 4.003 3 Li 6.941 4 Be 9.012 IIIB IVB VB VIB VIIB VIII IB IIB 5 B 10.811 6 C 12.011 7 N 14.007 8 O 15.999 9 F 18.998 10 Ne 20.180 11 Na 22.990 12 Mg 24.305 13 Al 26.982 14 Si 28.086 15 P 30.974 16 S 32.065 17 Cl 35.453 18 Ar 39.948 19 K 39.098 20 Ca 40.078 21 Sc 44.956 22 Ti 47.867 23 V 50.942 24 Cr 51.996 25 Mn 54.938 26 Fe 55.845 27 Co 58.933 28 Ni 58.693 29 Cu 63.546 30 Zn 65.409 31 Ga 69.723 32 Ge 72.64 33 As 74.921 34 Se 78.96 35 Br 79.904 36 Kr 83.798 37 Rb 85.468 38 Sr 87.62 39 Y 88.906 40 Zr 91.224 41 Nb 92.906 42 Mo 95.94 43 Tc (98) 44 Ru 101.07 45 Rh 102.906 46 Pd 106.42 47 Ag 107.868 48 Cd 112.411 49 In 114.818 50 Sn 118.710 51 Sb 121.760 52 Te 127.60 53 I 126.904 54 Xe 131.293 55 Cs 132.905 56 Ba 137.327 71 Lu 174.967 72 Hf 178.49 73 Ta 180.948 74 W 183.84 75 Re 186.207 76 Os 190.23 77 Ir 192.217 78 Pt 195.078 79 Au 196.967 80 Hg 200.59 81 Tl 204.383 82 Pb 207.2 83 Bi 208.980 84 Po (209) 85 At (210) 86 Rn (222) 87 Fr (223) 88 Ra 226.025 103 Lr (262) 104 Rf (261) 105 Db (262) 106 Sg (266) 107 Bh (264) 108 Hs (277) 109 Mt (268) 110 Ds (281) 111 Rg (272) 112 (285) 113 114 (289) 115 116 117 118 57 La 138.906 58 Ce 140.116 59 Pr 140.908 60 Nd 144.24 61 Pm (145) 62 Sm 150.36 63 Eu 151.964 64 Gd 157.25 65 Tb 158.925 66 Dy 162.500 67 Ho 164.930 68 Er 167.259 69 Tm 168.934 70 Yb 173.04 89 Ac 227.028 90 Th 232.038 91 Pa 231.036 92 U 238.029 93 Np 237.048 94 Pu (244) 95 Am (243) 96 Cm (247) 97 Bk (247) 98 Cf (251) 99 Es (252) 100 Fm (257) 101 Md (258) 102 No (259) Cn (284) (289) (294) (294) (291) d 6 d 5 Fe 4s 3d Fe 2+ 4s 3d Fe 3+ 4s 3d d 10 d 9 Cu 4s 3d Cu + 4s 3d Cu 2+ 4s 3d described by # valence d e – d e – first row M 2+ ions = Z – 20 Fl Lv “Even when they are saturated in the sense of the older theory of (primary) valence, the elementary atoms still possess sufficient chemical affinity to bind other seemingly also saturated atoms and groups of atoms, under generation of clearly defined atomic bonds. This doctrine has now been so amply confirmed experimentally by investigations of a very large number of molecular compounds which are now called complex compounds, that we can make it the starting-point of further developments.” Alfred Werner 1913 Nobel Prize Lecture Complex Compounds
21
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4/6/2015
1
Transition Metals in Coordination Chemistry IA VIIIA
1
H 1.008 IIA
IIIA IVA VA VIA VIIA
2
He 4.003
3
Li 6.941
4
Be 9.012
IIIB IVB VB VIB VIIB VIII IB IIB
5
B 10.811
6
C 12.011
7
N 14.007
8
O 15.999
9
F 18.998
10
Ne 20.180
11
Na 22.990
12
Mg 24.305
13
Al 26.982
14
Si 28.086
15
P 30.974
16
S 32.065
17
Cl 35.453
18
Ar 39.948
19
K 39.098
20
Ca 40.078
21
Sc 44.956
22
Ti 47.867
23
V 50.942
24
Cr 51.996
25
Mn 54.938
26
Fe 55.845
27
Co 58.933
28
Ni 58.693
29
Cu 63.546
30
Zn 65.409
31
Ga 69.723
32
Ge 72.64
33
As 74.921
34
Se 78.96
35
Br 79.904
36
Kr 83.798
37
Rb 85.468
38
Sr 87.62
39
Y 88.906
40
Zr 91.224
41
Nb 92.906
42
Mo 95.94
43
Tc (98)
44
Ru 101.07
45
Rh 102.906
46
Pd 106.42
47
Ag 107.868
48
Cd 112.411
49
In 114.818
50
Sn 118.710
51
Sb 121.760
52
Te 127.60
53
I 126.904
54
Xe 131.293
55
Cs 132.905
56
Ba 137.327
71
Lu 174.967
72
Hf 178.49
73
Ta 180.948
74
W 183.84
75
Re 186.207
76
Os 190.23
77
Ir 192.217
78
Pt 195.078
79
Au 196.967
80
Hg 200.59
81
Tl 204.383
82
Pb 207.2
83
Bi 208.980
84
Po (209)
85
At (210)
86
Rn (222)
87
Fr (223)
88
Ra 226.025
103
Lr (262)
104
Rf (261)
105
Db (262)
106
Sg (266)
107
Bh (264)
108
Hs (277)
109
Mt (268)
110
Ds (281)
111
Rg (272)
112
C (285)
113
C 12.011
114
C (289)
115
C 12.011
116
C (289)
117
C 12.011
118
57
La 138.906
58
Ce 140.116
59
Pr 140.908
60
Nd 144.24
61
Pm (145)
62
Sm 150.36
63
Eu 151.964
64
Gd 157.25
65
Tb 158.925
66
Dy 162.500
67
Ho 164.930
68
Er 167.259
69
Tm 168.934
70
Yb 173.04
89
Ac 227.028
90
Th 232.038
91
Pa 231.036
92
U 238.029
93
Np 237.048
94
Pu (244)
95
Am (243)
96
Cm (247)
97
Bk (247)
98
Cf (251)
99
Es (252)
100
Fm (257)
101
Md (258)
102
No (259)
Cn (284) (289) (294) (294) (291)
d 6
d 5
Fe 4s 3d
Fe2+ 4s 3d
Fe3+ 4s 3d
d 10
d 9
Cu 4s 3d
Cu+ 4s 3d
Cu2+ 4s 3d
described by # valence d e–
d e– first row M2+ ions = Z – 20
Fl Lv
“Even when they are saturated in the sense of the older theory
of (primary) valence, the elementary atoms still possess sufficient
chemical affinity to bind other seemingly also saturated atoms and
groups of atoms, under generation of clearly defined atomic bonds.
This doctrine has now been so amply confirmed experimentally by
investigations of a very large number of molecular compounds which
are now called complex compounds, that we can make it the
starting-point of further developments.”
Alfred Werner 1913 Nobel Prize Lecture
Complex Compounds
4/6/2015
2
F– fluoro
Cl– chloro
Br– bromo
I– iodo
CN– cyano
1. anionic ligands a. most have –o ending:
NO2 – nitro
OCN– cyanato
SCN– thiocyanato
CO32– carbonato
C2O42– oxalato
CH3COO– acetato
S2O32– thiosulfato
OH– hydroxo
NCO– isocyanato
NCS– isothiocyanato
H– hydrido
N3– azido
O22– peroxo
NO3– nitrato
O2– oxo
S2– thio
SH– mercapto
N3– nitrido
acetylacetonato
2,4-pentanedionato
acac
dimethylglyoximato
DMG
Mn+
Mn+
Nomenclature
N N O HO
O-N-O – nitrito
nitrito - N nitrito - O
thiocyanato - S thiocyanato - N
cyanato - O cyanato - N
H
O O
CH3– methyl
C6H5– phenyl
CH2 = CH– enyl
b. hydrocarbon anion –yl ending
cyclopentadienyl Cp
pentamethylcyclopentadienyl Cp*
Nomenclature
1. anionic ligands
allyl
(– H+)
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a. usually compound’s name
ethylenediamine en
N N
N N
bipyridine bipy
o-phenanthroline o-phen
H2O aqua
NH3 ammine
CO carbonyl
b. exceptions
NO nitrosyl
N2 dinitrogen
O2 dioxygen
H2N NH2
Nomenclature
2. neutral ligands
tri(R)phosphine
PPh3 P
R R
R
ethene (ethylene)
CH2
CH2
M
R = phenyl
PMe3 methyl
PtBu3 t-butyl
c. oxidation state
Roman numerals in parentheses: Stock notation
a. cationic or neutral complex
metal name unchanged
b. anionic complex
L form (usually like symbol) with –ate ending
cuprate ferrate aurate argenate
Alfred Stock
German
(1876-1946)
Nomenclature
3. metal
Cr3+
Fe2–
Ni
chromium(III)
nickel(0)
iron(–II)
no space!
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6. # of each ligand type with prefixes
a. short names di, tri, tetra, penta
b. long names bis, tris, tetrakis, pentakis
4. order
a. cation, anion
b. ligands first; attach directly to metal name
c. alphabetical order
5. a. neutral ligand name in parentheses
except for H2O, NH3, CO, NO
b. short anions not in parentheses
c. long anions (4 syllables) in parentheses
d. bridging ligands (2 metal ions) μ- (mu) before name