The reactivity of terminal chloroaminophosphido ligands towards metal carbonyl complexes. Formation of μ2- and μ3-phosphinidene clusters

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)NiPr2}] (3) with Co2(CO)8 lead to the heterobimetallic phosphinidene bridged compounds [CpMoCo(CO)5{μ-P(TMP)}] (4a) and [Cp*MoCo(CO)5{μ-P(NiPr2)}] (4b). Under photolysis, 1 and [CpMo(CO)3{P(Cl)NiPr2}] (2) react with Mn2(CO)10 and [CpMo(CO)3]2 to form the hetero- and homo-bimetallic phosphinidene bridged complexes [CpMoMn(CO)6(μ-PNR2)] (5a, NR2=TMP; b, NR2=NiPr2) and [{CpMo(CO)2}2{μ-PNR2}] (6a, b). Thermolysis of 1 with Ru3(CO)12 leads to the heterotrimetallic cluster [CpMoRu2(CO)8(μ-H){μ3-P(TMP)}] (7a), while thermolysis of 2 with Ru3(CO)12 leads to [CpMoRu2(CO)8(μ-H)(μ3-PNiPr2)] (7b) and the ruthenium clusters [Ru5(CO)15{μ4-PNiPr2}] (8), [Ru3(CO)9(μ-H)2(μ3-PNiPr2)] (9), and [Ru3(CO)9(μ3-PNiPr2)2] (10).