67415-75-2Relevant academic research and scientific papers
Synthesis, structure, and dynamic properties of bis(cis-(benzylthio)stilbenethiolate) complexes of nickel(II), palladium(II), and platinum(II) and of related compounds
Zhang, Cheng,Reddy, Hussain K.,Schlemper, Elmer O.,Schrauzer, Gerhard N.
, p. 4100 - 4103 (2008/10/08)
The products of the reactions of the bis(cis-stilbenedithiolates) of Ni(II), Pd(II), and Pt(II) with benzyl halides are shown to be chelates of cis-(benzylthio)stilbenethiolate by chemical degradation, independent synthesis, and X-ray structural analyses. The isolated solid trans-anti isomers of M[(PhCH2)2S4C4Ph4] (M = Ni, Pd, Pt) are isomorphous and crystallize in space group P21/c with Z = 2. For M = Ni, a = 14.832 (3) ?, b = 8.814(2) ?, c = 14.867 (3) ?, β = 112.69 (2)°, and dcalcd = 1.344 (2) g cm-3. For M = Pd, a = 14.898 (3) ?, b = 8.805 (3) ?, c = 14.791 (3) ?, β = 110.98 (2)°, and dcalcd = 1.42 g cm-3. For M = Pt, a = 14.885 (4) ?, b = 8.828 (3) ?, c = 14.806 (6) ?, β = 111.04 (2)°, and dcalcd = 1.58 g cm-3. The central metal atoms of the nickel complex are in a slightly distorted planar ligand environment. The C-S(CH2Ph) bond lengths of 1.835 (2) ? are longer than normal due to electronic labilization. The complexes show dynamic behavior in solution primarily due to sulfur inversion processes, as evidenced by variable-temperature 1H NMR measurements. The trans-anti and trans-syn isomers are the pre-dominant species in solutions of the nickel complexes. In solutions of the complexes of Pd and Pt, the cis-anti isomers were also detectable; the cis-anti isomer of the Pt complex is more stable than that of Pd and can be isolated. Also synthesized were several aralkyl and substituted-benzyl complexes of the type M[RCH2)2S4C4Ph4], with M = Ni and R = 4-naphthyl, 9-anthracenyl, 4-CH3OC6H4-, and 4-NO2C6H4-H4-. All aralkyl dithiolenes are light-sensitive in solution. In a series of complexes with M = Ni, the rates of photodecomposition, which proceeds with C-S bond homolysis, increase with increasing electronic labilization of the C-S(aralkyl) bonds.
