The reactivity of terminal chloroaminophosphido ligands towards metal carbonyl complexes. Formation of μ 2- and μ 3-phosphinidene clusters

Abstract

Reactions of the terminal molybdenum phosphido compounds [CpMo(CO) 2{P(Cl)TMP}] ( 1, TMP=2,2,6,6-tetramethyl-1-piperidyl) and [Cp*Mo(CO) 3{P(Cl)N iPr 2}] ( 3) with Co 2(CO) 8 lead to the heterobimetallic phosphinidene bridged compounds [CpMoCo(CO) 5{μ-P(TMP)}] ( 4a) and [Cp*MoCo(CO) 5{μ-P(N iPr 2)}] ( 4b). Under photolysis, 1 and [CpMo(CO) 3{P(Cl)N iPr 2}] ( 2) react with Mn 2(CO) 10 and [CpMo(CO) 3] 2 to form the hetero- and homo-bimetallic phosphinidene bridged complexes [CpMoMn(CO) 6(μ-PNR 2)] ( 5a, NR 2=TMP; b, NR 2=N iPr 2) and [{CpMo(CO) 2} 2{μ-PNR 2}] ( 6a, b). Thermolysis of 1 with Ru 3(CO) 12 leads to the heterotrimetallic cluster [CpMoRu 2(CO) 8(μ-H){μ 3-P(TMP)}] ( 7a), while thermolysis of 2 with Ru 3(CO) 12 leads to [CpMoRu 2(CO) 8(μ-H)(μ 3-PN iPr 2)] ( 7b) and the ruthenium clusters [Ru 5(CO) 15{μ 4-PN iPr 2}] ( 8), [Ru 3(CO) 9(μ-H) 2(μ 3-PN iPr 2)] ( 9), and [Ru 3(CO) 9(μ 3-PN iPr 2) 2] ( 10).