Abstract
A series of compounds trans-[PtH(R)(PPh3)2][R = C6H4Y-p(Y = Me, OMe, F, or Cl), C6H4Me-o, C6H3Cl2-2,5, C6HCl4-2,3,4,5, C6HCl4-2,3,4,6, C6Cl5, or C6F5], cis-[PtH(C6F5)(PPh3)2], and cis-[PtH(Ph)(dppe)](dppe = Ph2PCH2CH2PPh2) have been obtained by decarboxylation of formate complexes, or by the reaction of the halogeno complexes with NaBH4. The compounds have been characterized by i.r. and n.m.r. (1H, 31P, and 195Pt) spectroscopy. The molecular structure of trans-[PtH(C6H4F-p)(PPh3)2] has been determined by a single-crystal X-ray structural analysis. The crystals are orthorhombic, space group Pcab, with a= 25.304(5), b= 23.963(5), c= 11.530(3)Å, and Z= 8. Dimethyl acetylenedicarboxylate inserts into the Pt–H bond of trans-[PtH(R)(PPh3)2](R = C6H4Cl-p, C6H4Me-p, or C6H4Me-o) to give the corresponding σ-vinyl complexes, but other alkynes and olefins do not react. The thermal stability in solution has also been studied; decomposition takes place via reductive elimination to give RH. The results obtained are explained in terms of the electronegativity and the size of the ligands and the configuration of the complexes.
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