Parallels between main group and organometallic chemistry 7 electrons 17 electrons Electronically equivalent
Parallels between main group and organometallic chemistry
7 electrons 17 electrons
Electronically equivalent
Parallels between P and carbonyl complexes
Tetrahedral tetramers
Exceptions: IF7, XeF4 � no organometallic analogues;
ligands weaker than CO in the spectrochemical series
Roald Hoffmann in his 1981 Nobel lecture;
Hoffmann defined molecular fragments
to be isolobal
if the number, symmetry properties,
Isolobal Analogy
if the number, symmetry properties,
approximate energy and shape of the
frontier orbitals and the number of electrons
in them are similar-not identical, but similar.
Hoffmann, R. Angew. Chem. Int. Ed. 1982, 21, 711
Two “fragments” are called isolobal if their “working”
frontier orbitals, that is HOMO and LUMO:
i) are the same in number,
ii) have the same number of electrons on them;
iii) have similar shape and symmetry,iii) have similar shape and symmetry,
iv) are of approximately the same energy.
Isolobal fragments can replace each other in morecomplex structures and have similar bondingpatterns
Fragments with one working empty orbital:
All Lewis acids above can produce an adduct with aLewis base pyridine (py):
The isolobal species Ir(CO)3, Co(CO)3, CR, and P
Structures resulting from combinations of Co(CO)3 and CR
2. Gain or loss of electrons from two isolobal fragments yields isolobal fragments
1. The isolobal definition may be extended to isoelectronic fragments having the same coordination number
Mn(CO)5 CH3, Re(CO)5 CH3[Fe(CO)5]
+
[Cr(CO)5]-
Extensions of the analogy
17 electron 7 e 17 e 7 e
isolobal fragments
Mn(CO)5 CH3, Cr(CO)5 CH3+
Mo(CO)5W(CO)5
Fe(CO)5 CH3-
Ru(CO)5Os(CO)5
Fe(CO)5 and CH4 are not isolobal – reason it out
17 e 7 e 16 e 6 e
18 e 8 e
3. Other 2-electron donors are treated similarly to CO
4. Ligands η5-C5H5 and η6-C6H6 are considered to occupy
three coordination sites and to be 6-electron donors
Mn(CO)5 Mn(PR3)5 MnCl55– Mn(NCR)5 CH3
(η6-C6H6)Mn(CO)2 Mn(CO)5 CH3
(η5-C5H5)Fe(CO)2 Fe(CO)5+ CH3
(η5-C5H5)Mn(CO)2, (η6-C6H6)Cr(CO)2, [Mn(CO)5]
+, Cr(CO)5
5. Octahedral fragments of formula MLn (where M has a dx configuration)are isolobal with square-planar fragments of formula MLn-2 (where M hasa dx+2 configuration and L is a 2-electron donor).
Octahedral Fragments Square-planar FragmentsMLn MLn-2Cr(CO)5 PtCl3
-
d6 d8
Fe(CO) Pt(PR )Fe(CO)4 Pt(PR3)2d8 d10
5. Octahedral fragments of formula MLn (where M has a dx configuration)are isolobal with square-planar fragments of formula MLn-2 (where M hasa dx+2 configuration and L is a 2-electron donor). Comparison of square-planar fragments with octahedral fragments
Square planar d8
ML3 has an emptylobe of anonbonding hybridorbital as a LUMO
Comparison of square planar fragments with octahedral fragments
orbital as a LUMO[PtCl3]
–; similarly,octahedral d6 ML5fragment [Cr(CO)5],thus the isolobalanalogy between thetwo
d10 ML2 fragment [Pt(PR3)2] would have 2 valence electrons
more than PtCl2
These electrons occupy two nonbonding hybrid orbitals
This situation is comparable to Fe(CO)4 fragmet; each
complex has two singly occupied lobes
The 5-electron fragment CH is isolobal with P and other Group 15atoms. A potential application of this relationship is to seekphosphorus-containing analogues to organometallic complexescontaining cyclic ligands such as C5H5 and C6H6
Examples of applications of the analogy
Angew. Chem. Int. Ed. 1987, 26, 59 Science 2002, 295, 832