The reaction of P 4 with [Cp′Mo(CO) 3] 2 (Cp′ = η5-C 5H 4tBu)—the structure of [Cp′Mo(CO) 2

Abstract

The photochemical reaction of [Cp′Mo(CO) 3] 2 (Cp′ = η 5-C 5H 4 tBu) with white phosphorus in the presence of [Cr(CO) 5thf] leads to the P n ligand complexes [Cr(CO) 4 <( η 4-P 4){(Cr(CO) 5} 4>;] ( 1), [Cp′Mo(CO) 2<( η 3-P 4){Cr(CO) 5 4(H)>] ( 2) and [{Cp′Mo(CO) 2} 2<( μ, η 2-P 2){Cr(CO) 5} 2>] ( 3). The products were characterized by NMR, IR and partially by X-ray structure analysis. The reaction proceeds via a PP bond cleavage leading to the bent cyclo-P4 complex [Cp′Mo(CO) 2<( η 3-P 4){Cr(CO) 5} 4{Cp′Mo(CO) 3}>] ( 2a), which hydrolysis during the chromatographic work-up to give the more stable compound 2. Furthermore, a P 3 P 1 fragmentation of 2a occurs to form the phosphido complex intermediate [CP′CO) 2MoP → Cr(CO) 5]. The latter dimerises resulting in the formation of the tetrahedral compound 3, containing a Mo 2P 2 moiety.