Crystal and molecular structure and ³¹P and ¹⁹⁵Pt nmr spectroscopy of [Pt₃S₂(PMe₂Ph)₆][BEt₄]₂; a trinuclear complex containing triply-bridging sulphide ligands

Abstract

An X-ray diffraction study of [Pt3S2(PMe2Ph)6][BEt4]2 shows that it crystallises in the monoclinic space group, C2/c, with a = 15.447(2), b = 18.033(3), c = 26.505(5) Å, β = 96.73(2)°. The cation consists of three, distorted, square-planar cis-PtS2(PMe2Ph)2 moieties combined by sharing of the two sulphur atoms to produce a central Pt3S2 unit with C2 symmetry and Pt—Pt distances of 3.182(1) Å (one edge) and 3.108(1) Å (two edges). Complete analysis and computer simulation of 31P{1H} and 195Pt{1H} nuclear magnetic resonance spectra give values for 1J(Pt—P), 3202 Hz; 3J(Pt—P), −25 Hz; and 2J(Pt—Pt), 476 Hz. The structure is compared with previous results for analogous Ni and Pd complexes and the structural and nmr parameters are discussed with reference to the possibility of metal–metal interactions.

Unusual C−H Allylic Activation in the {PtII(cod)} Fragment Bonded to a {Pt2(μ-S)2} Core

“…However, deviation from the ideal geometry is evidenced by the dihedral angles between pairs of the three PtS 2 planes, which range from 114.4° to 124.8°. The geometric features of the Pt 3 S 2 unit compare well with those observed in the [{Pt 2 (μ 3 -S) 2 (dppp) 2 }Pt(C 8 H 11 )] + derivative, described below, and with related complexes containing the P 6 Pt 3 S 2 core with monodentate and chelating phosphine ligands. 8b,, Moreover, the overall structure of [{Pt 2 (μ 3 -S) 2 (dppp) 2 }Pt(cod)] 2+ bears a close resemblance to that of its selenium analogue containing a Pt 3 Se 2 core 5 Molecular structure of 1 with the key atoms labeled and 50% probability ellipsoids.…”