Reaction of a heterotopic P,SAs ligand with group 10 metal(ii) complexes: As–S bond cleavage and the formation of two unusual trinuclear structural isomers for Pd and Pt
作者:Imola Sárosi、Alexandra Hildebrand、Peter Lönnecke、Luminiţa Silaghi-Dumitrescu、Evamarie Hey-Hawkins
DOI:10.1039/c2dt12506d
日期:——
The synthesis of the heterotopic P,SAs ligand, 1-Ph2AsSC6H4-2-PPh2 (1) and its reaction with [PdCl2(cod)], [PtI2(cod)] (cod = 1,5-cyclooctadiene) and NiCl2·6H2O is reported. Cleavage of the AsâS bond of 1 and coordination of the resulting phosphanylthiolato ligand (SC6H4-2-PPh2)â (SC6H4-2-PPh2 = P,S) was observed with formation of [M(P,S)2] (M = Ni, Pd, Pt). In the case of Pd and Pt, not only the mononuclear complexes [M(P,S)2] formed, but also the trimers of [MX(P,S)] ([MX(μ-S-SC6H4-2-PPh2)-κ2S,P}]3 [M = Pd, X = Cl (2) and M = Pt, X = I (4)]). Formation of 2 and 4 was preceded by the trinuclear isomeric intermediates [(cis-M(μ-S-SC6H4-2-PPh2)-κ2S,P}2)-MX2-MX(μ-S-SC6H4-2-PPh2)-κ2S,P}] [M = Pd, X = Cl (3) and M = Pt, X = I (5)]. The crystal structures of 1â5 and a possible reaction mechanism that leads to 2 and 4 are presented.
报告了异位 P,SAs 配体 1-Ph2AsSC6H4-2-PPh2 (1) 的合成及其与 [PdCl2(cod)]、[PtI2(cod)](cod = 1,5-环辛二烯)和 NiCl2Â-6H2O 的反应。观察到 1 的 AsâS 键断裂,由此产生的膦酰硫配体 (SC6H4-2-PPh2)â (SC6H4-2-PPh2 = P,S)配位,形成 [M(P,S)2] (M = Ni、Pd、Pt)。在钯和铂的情况下,不仅形成了单核配合物[M(P,S)2],还形成了[MX(P,S)]的三聚体([MX(δ-SC6H4-2-Ph2)-δ2S,P}]3 [M = 钯,X = Cl (2) 和 M = 铂,X = I (4)])。在形成 2 和 4 之前,先出现了三核异构中间体[(cis-M(δ-SC6H4-2-Ph2)-δ2S,P}2)-MX2-MX(δ-SC6H4-2-Ph2)-δ2S,P}][M = Pd, X = Cl (3) 和 M = Pt, X = I (5)]。本文介绍了 1â5 的晶体结构以及生成 2 和 4 的可能反应机理。