Formation of new cluster derivatives of triphospholene via ligand substitution and cleavage of P-P bond(s)

摘要

At room temperature, triphopholene PhPPhPPhPCPh=CPh (L) underwent mono- and di-substitution reactions with [Os_3(CO)_(11)(MeCN)] to afford the following derivatives: mono-substituted cluster [Os_3(CO)_(11)(2-PhPPhPPhPCPh=CPh)] 1, di-substituted bridged cluster [Os_3(CO)_(10)(1,3-PhPPhPPhPCPh=CPh)] 2, and linked cluster [{Os_3(CO)_(11)}_2(1,3-PhPPhPPhPCPh=CPh)] 3. On the other hand, reactions with [Os_3(CO)_(10)(MeCN)_2] gave two isomeric compounds: 2 and [Os_3(CO)_(10)(1,3-PhPPhPPhPCPh=CPh)] 4, differing in the orientation of the phenyl group attached to the central unco-ordinate phosphorus atom. At elevated temperatures similar reactions result in cleavage of one P-P bond of the ligand to afford an open cluster [Os_3(CO)_9(#mu#_3-#eta#~3-PhPPhPCPh=CPhPPh)] 5, and cleavage of two P-P bonds to give [Os_3(CO)_9(#mu#_3-PPh)(#mu#_3-#eta#~2-PhPCPh=CPhPPh)] 6, arising from the formation of the phosphinidene species. The clusters 1, 2 and 4 can be converted sequentially on heating into 5 and then 6.