Department of Chemistry, Faculty of Sciences, Shiraz University, Shiraz 71454 Iran.
Inorg Chem. 2010 Sep 20;49(18):8435-43. doi: 10.1021/ic1010067.
The reaction of phthalazine with the binuclear organoplatinum complexes [Me(2)Pt(μ-SMe(2))(μ-dppm)PtR(2)], R = Me, Ph, 4-tolyl or R(2) = (CH(2))(4), dppm = bis(diphenylphosphino)methane, gives the corresponding complexes [Me(2)Pt(μ-phthalazine)(μ-dppm)PtR(2)] by displacement of the bridging dimethylsulfide ligand. The structures of [Me(2)Pt(μ-SMe(2))(μ-dppm)PtMe(2)] and [Me(2)Pt(μ-phthalazine)(μ-dppm)PtMe(2)] have been determined. Kinetic studies show that the reactions occur mostly by a second order reaction when R = Me or R(2) = (CH(2))(4) but entirely by a first order reaction when R = Ph or 4-tolyl. Evidence is presented that the reactions when R = Me or R(2) = (CH(2))(4) can occur by either associative or dissociative mechanisms but that the reactions when R = Ph or 4-tolyl occur only by an unusual dissociative mechanism involving formation of an intermediate with a donor-acceptor Pt-Pt bond.
哒嗪与双核有机铂配合物[Me(2)Pt(μ-SMe(2))(μ-dppm)PtR(2)]（R = Me、Ph、4-甲苯基或 R(2) = (CH(2))(4)，dppm = 双（二苯基膦）甲烷）反应，通过取代桥联二甲硫醚配体得到相应的配合物[Me(2)Pt(μ-phthalazine)(μ-dppm)PtR(2)]。[Me(2)Pt(μ-SMe(2))(μ-dppm)PtMe(2)]和[Me(2)Pt(μ-phthalazine)(μ-dppm)PtMe(2)]的结构已被确定。动力学研究表明，当 R = Me 或 R(2) = (CH(2))(4)时，反应主要通过二级反应发生，但当 R = Ph 或 4-甲苯基时，反应完全通过一级反应发生。有证据表明，当 R = Me 或 R(2) = (CH(2))(4)时，反应可以通过缔合或解离机制发生，但当 R = Ph 或 4-甲苯基时，反应仅通过涉及形成具有供体-受体 Pt-Pt 键的中间体的不寻常解离机制发生。
