Transition metal–carbon bonds. Part 53. The further chemistry of cyclometallated complexes formed from But2P(CH2)5PBut2 and PtCl2 : crystal structure of [PtCl{But2PCH2CH2CCHCH2PBut2}]

Abstract

The cyclometallated complex [[graphic omitted]Bu^t₂}](1a) reacts with CO, CNMe, or CNBu^t(Y) in the presence of NaBPh₄ to give the salts [[graphic omitted]Bu^t₂}][BPh₄](2). The carbonyl complex when treated with NaOMe gives the hydride [[graphic omitted]Bu^t₂}]. We have previously reported that [PtCl₂(NCBu^t)₂] reacts with Bu^t₂P(CH₂)₅PBu^t₂ to give a number of species, including (1 a) inseparably mixed with another complex. We have now separated this complex and identified it as [[graphic omitted]Bu^t₂}](3). The compound Ph₃C⁺BF₄^– converts (1a) into the olefin complex [[graphic omitted]Bu^t₂}][BF₄](5). Attempts to deprotonate (5) and other complexes with various bases, to give (3), were unsuccessful; various products were formed for which some structures are suggested. Crystals of (3) are monoclinic, space group P2₁/c, with a= 1.2319(3), b= 1.4370(4), c= 1.4693(3) nm, and β= 104.58(2)°. The structure was determined from 2 457 F_o and refined to R= 0.049. The molecule is disordered.