Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
15-1 Main group parallels with binary carbonyl complexes 15-2 The isolobal analogy 15-3 Metal-metal bonds 15-4 Cluster compounds
7 electrons
17 electrons
Electronically equivalent
Tetrahedral tetramers
Ronal Hoffmann in his 1981 Nobel lecture; Hoffmann defined molecular fragments to be isolobal 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.
Cyclic trimers
Mn(CO)5
CH3,
CH3
2. Gain or loss of electrons from two isolobal fragments yields isolobal fragments.
Mn(CO)5
CH3,
CH3+
CH3-
Mn(CO)5
Mn(PR3)5
[MnCl5]5-
Mn(NCR)5
CH3
4. Ligands 5-C5H5 and 6-C6H6 are considered to occupy three coordination sites and to be 6-electron donors
(6-C6H6)Mn(CO)2 (5-C5H5)Fe(CO)2
Mn(CO)5 [Fe(CO)5]+
CH3, CH3,
The 5-electron fragment CH is isolobal with P and other Group 15 atoms. A potential application of this relationship is to seek phosphorouscontaining analogues to organometallic complexes containing cyclic ligands such as C5H5 and C6H6
eclipsed
staggered
Structures ?
Relative energies of orbitals
The effect of population of and * orbitals on bond distances can sometimes be surprisingly small.
Formal shortness ration = 0.774 - Trans-bent geometry and apparent interactions Science, 2005 JACS, 2007
Influence of bridging ligands Nonlinearity More complex interactions Angew. Chem. Int. Ed., 2008
15-4-1 Boranes
Each boron has four valence orbitals ---- total 24 boron orbitals s and 3p
13 bonding orbitals (= 2n + 1) 7 bonding orbitals (= n + 1) 6 bonding orbitals (= n) boron-hydrogen bonding 11 nonbonding or antibonding orbitals
15-4-1 Boranes
15-4-1 Boranes
15-4-1 Boranes
15-4-2 Heteroboranes
Isoelectronic species such as the carboranes (carbaboranes) CH+ unit is isoelectronic with BH.
15-4-2 Heteroboranes
Therefore closo
As ligand
Related to the classification of the structure as closo, nido Four valence orbitals Nine valence orbitals
Five extra orbitals 10 more electrons per framework atom
Seven metal-metal framework bonding pairs are the most common Metal cores for clusters containing seven skeletal bond pairs.
Co4(CO)12
60 valence electrons
nido
Carbon exhibits unusual coordination numbers and geometries not found in classic organic structures
Carbide clusters
86 electrons
Encapsulated iron
Homework