Acetylene incorporation into the spiked framework of the phosphinidene and arsinidene clusters [Ru_4(CO)_13(#mu#-H)_2(#mu#_4ECF_3)] (E = P or As): skeletal rearrangement and crystal structures of a series of tetranuclear ruthenium clusters bearing al

摘要

Reactions of [Ru_4(Co)_(13)(#mu#-H)_2(#mu#_4-ECF_3)] (E = P 1 or As 2) with RC ident to CR (R = Ph or H) under mild conditions yielded square planar clusters [Ru_4(CO)_9(#mu#-CO)_2(#mu#_4-ECF_3)(RC_2R)] (E = As, R = Ph 3; E = P, R = Ph 4 or E = P, R = H 5) in which the acetylene ligands are attached to the metal square planes via 2#sigma# + 4#pi# bonds. Under similar conditions, the reaction of 1 with CF_3C ident to CCF_3 afforded a similar cluster [Ru_4(CO)_(12)(#mu#_4-PCF_3)(CF_3_2CF_3)] 6 in which the acetylene interacts with the Ru_4 square face only by 4#sigma# bonds. Reactions of 1 and 2 with MeC ident to CMe resulted in metal skeletal rearrangement and P-C bond formation to form the butterfly cluster [Ru_4(CO)_(10)(#mu#-CO)_2{CF_3PC(Me)C(Me)}] 7 and alkyne dimerization at thespiked Ru atom to form spiked clusters [Ru_4(CO)_9(#mu#-CO)_2(#mu#_4-ECF_3)(C_4Me_4)] (E = p 8 or As 9) containing a metallocyclic RuC_4Me_4 ring. Reaction of 1 with diphenylbutadiyne under similar conditions afforded a square planar cluster [Ru_4(CO)_(11)(#mu#_4PCF_3){PhC(H)C(H)CCPh}] 10 where the bridging hydrogen migrates to the diyne to form a 1,4-diphenylbut-3-en-1-yne fragment attached to the Ru_4 face.