By Robert H. Crabtree
Totally up to date and elevated to mirror fresh advances, this Fourth variation of the vintage textual content offers scholars chemists with an exceptional creation to the foundations and normal houses of organometallic compounds, in addition to together with useful info on response mechanisms and distinctive descriptions of up to date purposes.
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Additional info for The Organometallic Chemistry of the Transition Metals, 4th Ed.
To avoid misunderstandings it is therefore necessary to specify the resonance form to which the formal oxidation state applies. For neutral ligands like butadiene, the neutral L2 form is generally used because this is the stable form of the ligand in the free state. 15. Clearly, we can place no reliance on the formal oxidation state to tell us about the real charge on the metal in W(butadiene)3 . 2) several ways in which we can learn something about the real charge. In spite of its ambiguities, the oxidation state convention is almost universally used in classifying organometallic complexes.
The metals are more electron rich, in the sense that the metal bears a greater negative charge in the organometallic complex. 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.
For example, the odd number for Cp2 Fe+ implies paramagnetism because in a mononuclear complex we cannot pair five electrons whatever the d-orbital splitting. 8) Many organometallic compounds have low or intermediate formal oxidation states. High oxidation states are now gaining more attention and in Chapters 11 and 15, we look at these interesting species in detail. Back donation is severely reduced in higher oxidation states because (1) there are fewer (or no) nonbonding d electrons available and (2) the increased partial positive charge present on the metal in the high-oxidation-state complex strongly stabilizes the d levels so that any electrons they contain become less available.