74353-70-1Relevant academic research and scientific papers
Synthetic and spectroscopic studies into the mechanism of the [Pt(PR3)4]/R2P(S)H reaction. Formation and structure of the novel diplatinum(II) dihydride complex [Pt2(H)2(P-t-Bu3)2(μ-SPPh 2)2]
Rahman,Ceccarelli,Oliver,Messbauer,Meyer,Walther
, p. 2355 - 2359 (2008/10/08)
The reaction of [Pt(PR′3)4] (R′ = alkyl, phenyl) with Ph2P(S)H yields the diplatinum(I) complexes [Pt2(PR′3)2(μ-SPPh2) 2]. The reaction proceeds via the isolable intermediate [PtH(PR′3)2{P(S)Ph2}] which exists in solution as a mixture of the trans and cis isomers. Both isomers lose one phosphine ligand at higher temperatures, yielding coordinately and electronically unsaturated species that form the final diplatinum(I) complexes. The intermediates have been characterized by NMR spectroscopy and the results discussed in comparison to the reaction of [Pt(PR′3)4] with Ph2P(O)H. [Pt(P-t-Bu3)2] and Ph2P(S)H react unexpectedly to give the novel diplatinum(II) complex [Pt2(H)2(P-t-Bu3)2(μ-SPPh 2)2] which has been characterized by 31P and 1H NMR spectroscopy and by a single-crystal structure determination. It crystallizes in the monoclinic system, space group C2/c, with cell dimensions of a = 18.063 (1) A?, b = 16.572 (1) A?, c = 17.318 (1) A?, β = 92.240 (5)°, V = 5180.1 (6) A?3, and Z = 4. Full-matrix least-squares refinement on 2362 data gave R = 3.5% and Rw = 4.6%. The structure determination has shown that the platinum(II) atoms have square-planar geometry surrounded by bridging S and P atoms and terminal P and H atoms and that the Pt-S-P(1)′-Pt′-S′-P(1) unit is in a boat conformation. Each of the Pt-S-P(1)′-Pt′ units is planar. The planar atoms in the dimer are 3.620 (1) A? apart, ruling out the possibility of metal-metal interactions. The other distances around Pt are as follows: Pt-S = 2.451 (3) A?, Pt-P(1)(bridge) = 2.285 (3) A?, Pt-P(2)(terminal) = 2.330 (3) A?, and Pt-H(66) = 1.42 A?.
