By Gould R.F. (ed.)

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The M−L bonds are much more covalent and often have a substantial π component. The metal d orbitals are higher in energy and by back donation perturb the electronic structure of the ligands much more than is the case for coordination compounds. The organometallic ligands can be polarized and therefore activated toward chemical reactions, σ and π bonds in the ligands can be weakened or broken, and chemical bonds can be made or broken within and between different ligands. This rich pattern of reactions is characteristic of organometallic chemistry.

6), cancel out. Formation of the M−CO bond weakens the C−O bond relative to free CO. This will still lead to a stable complex as long as the energy gained from the M−C bond exceeds the loss in C−O. Bond weakening in L on binding is a very common feature in many M−L systems. Frontier Orbitals The picture for CO holds with slight modifications for a whole series of π acceptor (or soft) ligands, such as alkenes, alkynes, arenes, carbenes, carbynes, NO, N2 , and PF3 . Each has a filled orbital that acts as a σ donor and an empty orbital that acts as a π acceptor.

The d 0 oxidation state cannot back bond because it lacks d electrons, while a d 2 state often has an exceptionally high back-bonding power because early in the transition series the d orbitals are relatively unstable for the reasons mentioned above. The d 0 Ti(IV) species (C5 H5 )2 TiCl2 therefore does not react with CO at all, while the corresponding d 2 Ti(II) fragment, (C5 H5 )2 Ti, forms a very stable monocarbonyl, (C5 H5 )2 Ti(CO), with a very low ν(CO), indicating very strong back bonding.

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