Organotransition metal ligand coordination

The purpose of this review is to provide the reader with a scenario of what can be accomplished with nickel complexes. It is useful to do this via a series of broad schemes, hypothetical in some cases, which show the main reaction patterns, without considering mechanistic details. Examples will illustrate the various processes, but extension to other substrates or to different conditions often requires use of alternative ligands or solvents, or a change from a neutral complex to a cationic or anionic species, as indicated above. For references to syntheses with nickel see Baker et al. (10). For criteria for the synthesis of coordination compounds and stability of organotransition metal complexes in general, see references (11. 12). Organometallic literature has been collected periodically by Bruce (13). 

To summarize, the special bonding characteristics of 7r-acceptor ligands in organotransition metal compounds enable these complexes to coordinate small molecules such as ethylene, CO, and H2 and also provide an electronic buffer system to facilitate changes of metal oxidation state and coordination... 

Organotransition metal compounds have been known for over a century hut it has been only during the past 15 years that most of the major advances in this area have been made, Organotransition metal compounds consist of organic molecules or ligands coordinated to transition metals by one or more carbon atoms. In the present survey, the formation, properties, structure, and reactions of various classes of these substances are discussed. Emphasis has been placed on important discoveries and theories that have stimulated the rapid progress of organotransition metal chemistry. Pertinent reviews on various aspects of this subject have also been cited. 

This method was later extended to dienes and represents an early example of an important synthetic route in organotransition metal chemistry wherein one neutral ligand displaces another from the coordination sphere of a transition metal. 

A series of heterodinuclear late organotransition metal complexes (dppe)RPt-M(C0)4 (M = Mn, Re) show the unexpected regio- and seteroselective desulfurization of thiiranes controlled by the ancillary alkyl ligand (Scheme 3.69) [133]. Reaction of the methyl complex, (dppe)MePt-M(CO)4 with cis- and trans-2-butene sulfide results in the insertion of the thiirane into the Pt-M bond followed by the CO insertion into the carbon-M bond and coordination of the S atom to the... 

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