Addition of Pt(PBu^t₃) to Osmium−Tin Cluster Complexes

The reactions of the osmium−tin cluster complexes Os3(CO)12(μ3-SnPh)Ph, 9, and Os4(CO)16(μ4-Sn), 10, with Pt(PBut3)2 have been investigated. Two products, PtOs3(CO)12(Ph)(PBut3)(μ3-SnPh), 11, and Pt2Os3(CO)12(μ2-Ph)(PBut3)2(μ3-SnPh), 12, were obtained from the reaction of 9 with Pt(PBut3)2. These are mono- and bis-Pt(PBut3) adducts of 9 formed by the addition of a Pt(PBut3) group to the Os−Os bond in 11 and the Os−Os bond and Os−C bond to the σ-bonded phenyl group in 12. A PBut3 derivative of 11, Os2(CO)8(μ3-SnPh)Os(CO)3(PBut3)Ph, 13, was obtained by treating 12 with PBut3. The reaction of 10 with Pt(PBut3)2 provided the bis-Pt(PBut3) adduct Os4(CO)16[Pt(PBut3)]2(μ4-Sn), 14, that was formed by the addition of a Pt(PBut3) group across the Os−Os bond of both Os2(CO)8 groups in 10. All four new compounds 11−14 were characterized by single-crystal X-ray diffraction analysis.本研究考察了锇-锡团簇配合物Os3(CO)12(μ3-SnPh)Ph（化合物9）与Os4(CO)16(μ4-Sn)（化合物10）和二(三叔丁基膦)合铂（Pt(PBut3)2）的反应。化合物9与Pt(PBut3)2反应后，得到两种产物：PtOs3(CO)12(Ph)(PBut3)(μ3-SnPh)（化合物11）与Pt2Os3(CO)12(μ2-Ph)(PBut3)2(μ3-SnPh)（化合物12）。二者分别为化合物9的单取代和双取代Pt(PBut3)加合物：其中11是通过在Os-Os键上加成一个Pt(PBut3)基团制得，12则是同时在Os-Os键与σ键合苯基上分别接入Pt(PBut3)基团得到。将化合物12与三叔丁基膦（PBut3）反应，得到化合物11的PBut3衍生物Os2(CO)8(μ3-SnPh)Os(CO)3(PBut3)Ph（化合物13）。化合物10与Pt(PBut3)2反应则生成双Pt(PBut3)加合物Os4(CO)16[Pt(PBut3)]2(μ4-Sn)（化合物14），该产物是通过在10中两个Os2(CO)8单元的Os-Os键上各加成一个Pt(PBut3)基团生成。上述四种新化合物11~14均通过单晶X射线衍射分析完成了结构表征。