The terminal electrophilic phosphinidene complex [CpFe(CO) 2 {PN-i-Pr 2 }][AlCl 4 ] (2), generated via chloride abstraction from [CpFe(CO) 2 {P(Cl)N-i-Pr 2 }] (1), reacts with primary, secondary, and tertiary silanes to form the silyl phosphine complexes [CpFe(CO) 2 {P(H)(SiR 3 )N-i-Pr 2 }][AlCl 4 ] (3, SiR 3 =SiPhH 2 ; 4, SiR 3 =SiPh 2 H; 5, SiR 3 =SiEt 3 ), in which the phosphinidene has inserted into the Si-H bond. A computational study shows that the insertion is concerted and has a triangular transition state. The silyl phosphine complexes 3, 4, and 5 are very susceptible to nucleophilic attack, which leads to P-Si bond cleavage and formation of the bridging phosphido complex [{CpFe-(CO)} 2 (μ-CO){μ-P(H)N-i-Pr 2 }][AlCl 4 ] (6).

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