Platinum complexes hydrocarbyl

Look JL, Wick DD, Mayer JM, Goldberg KI. Autoxidation of platinum(IV) hydrocarbyl hydride complexes to form platinum(IV) hydrocarbyl hydroperoxide. Inorg Chem. 2009 48 1356-1369. 

Insertion of carbon monoxide and alkenes into metal-carbon bonds is one of the most important reaction steps in homogeneous catalysis. It has been found for insertion processes of platinum [16] that the relative positions of the hydrocarbyl group and the unsaturated fragment must be cis in the reacting complex [17], The second issue concerns the stereochemical course of the reaction, insertion versus migration as discussed in Chapter 2.2. 

Abstract Square-planar palladium(II) and platinum(II) complexes with a high-lying filled d 2 orbital can act as metalloligands for Lewis-acidic metal centers such as d ° and s cations. This behavior is promoted by hard ligands such as a-bound hydrocarbyl ligands. A wide diversity of structural motifs based on this kind of donor-acceptor metal-metal bonds has been discovered in the last decades. This chapter reviews the coordination chemistry of metalloligands derived from alkyl, aryl, alkynyl, and carbene complexes of palladium(II) and platinum(II). The specific reactivity of the resulting bimetallic complexes is also addressed. 

The chemistry of bimetallic complexes, in particular species containing hydrocarbyl bridging ligands, has experienced a notable development in recent years.Several reviews on the subject have appeared, and therefore only salient examples having 7 -olefinic platinum-bonding interactions will be considered here. 

Five coordinate platinum-alkene-hydrido complexes of the type [Pt(2,9-dimethyl-l,10-phenanthroline)(X)(H)(cjs-Me02CCH=CHC02Me)] (X = Cl, Br, I) can, in some cases, be isolated from reaction of the protic acid with [Pt(2,9-dimethyl-l,10-phenanthroline)(cw-Me02CCH=CHC02Me)]. In other cases insertion of the alkene into the Pt-H bond leads to the formation of four coordinate hydrocarbyl derivatives 5. 

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