Cyclopentane reaction with transition metal complexes

The mechanism for the reaction catalyzed by cationic palladium complexes (Scheme 24) differs from that proposed for early transition metal complexes, as well as from that suggested for the reaction shown in Eq. 17. For this catalyst system, the alkene substrate inserts into a Pd - Si bond a rather than a Pd-H bond [63]. Hydrosilylation of methylpalladium complex 100 then provides methane and palladium silyl species 112 (Scheme 24). Complex 112 coordinates to and inserts into the least substituted olefin regioselectively and irreversibly to provide 113 after coordination of the second alkene. Insertion into the second alkene through a boat-like transition state leads to trans cyclopentane 114, and o-bond metathesis (or oxidative addition/reductive elimination) leads to the observed trans stereochemistry of product 101a with regeneration of 112 [69]. 

In contrast to the reactions catalyzed by Group Vm transition metal complexes (see Section II.A. 1), the hydrosilylation of 1,5- or 1,6-dienes with H3SiPh catalyzed by Cp2 NdCH(SiMe3)2 results in the formation of (silylmethyl)cyclopentanes (336) via 5-exo carbocyclization (equation 137)46. 

Prior to 1982, Crabtree s report of the reaction of cyclopentane with a solvated IrH2(PPh3)2+ species to give a cyclopentadienyl-iridium product stood as the only well characterized example of a reaction of an alkane with a homogeneous transition metal, in contrast to the widespread reactivity of arenes [2]. Based upon the instability of the platinum methyl hydride complex Pt(PPh3)2(CH3)H, it was believed that alkane oxidative addition might not be a thermodynamically feasible process, and consequently few attempts were made to attempt such a reaction [3]. It was not until the discovery of the formation of stable alkane oxidative addition products in 1982 that it was realized that reactions of hydrocarbons were in fact feasible. 

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