1 ,l-Dimethylcyclopentane is dehydrogenated to form [(q4-C5H4Me2)lrL2]+ [L = ( P -F C ~H ~) ~P ] and then rearranged to give [(q5-C5H4Me)lr(Me)L21+ by [lrH2(Me2C0)2L21+, the first case of homogeneous C-C bond cleavage starting from an alkane with a transition metal complex.Our interest in the co-ordination chemistry of alkanes' has led us to look for ways of selectively breaking C-C bonds with a transition metal complex. We have been unable to do this in one step, but have developed a two-step route (Scheme l), involving prior dehydrogenation, followed by alkyl migration.2Neat 1,l-dimethylcyclopentanet (1) reacts with [IrH2-(Me2CO),{ (p-FC6H4)3P}2]SbF6 (2) and t-butylethylene (tbe) at 150°C over 8 h to give, among other products, a ' F 1,l-Dimethylcyclopentane (labelled as 99.993% pure) was supplied by the American Petroleum Institute, Carnegie Mellon University. No dimethylcyclopentenes (<0.01%) were detected by g.c. The reactions were carried out in a resealable 5 ml glass pressure vessel in vucuo with 0.4 ml of hydrocarbon, 100 pl(0.77 mmol) of tbe, and 100 mg (0.11 mmol) of metal complex. Products were detected and quantified by IH n.m.r. spectroscopy (90 or 500 MHz) and characterised by spectral and analytical data. The reactions do not involve metallic Ir, as judged by the usual tests (ref. 4; D. R. Anton and R. H. Crabtree, Organornetullics, 1983,2,855). In particular, the yields are unaffected by the presence of metallic Hg.
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