[CR(CO)
<sub>5</sub>
PCl
<sub>3</sub>
] — A Starting Material for Phosphorus‐Rich P
<sub>x</sub>
Ligand Complexes
作者:Manfred Scheer、Kay Schuster、André Krug、Helmut Hartung
DOI:10.1002/cber.19971300919
日期:1997.9
Abstract[Cr(CO)5PCl3] reacts with different metallates K[CpxMo(CO)3] [Cpx = ·5‐C5H4tBu (Cp]), ·5‐C5H3tBu2‐1,3 (Cp))], K[CpFe(CO)2], K[Cp]Cr(CO)3], K[C}*Ni(CO)] and Na2[Cr2(CO)10] at –78°C in THF to yiel various P2, cyclo‐ P3 and cyclo‐P5 ligand complexes of the formulae [Cp] Mo(CO)2 (.2‐P3)] (1a), [Cp]Mo(CO)2(.3‐P3)] (1b), [CP'Mo‐(CO)2}2(μ,.2‐P2)] (2a), [Cp]Mo(CO)2}2(μ, ·2‐P2)] (2b), [Cp]Fe).5‐P5)] (3), [(Cp'Cr)2(μ,.5‐P5)] (4), [Cp]Cr(CO)2}2‐(μ,.2‐P2)] (5), [(Cp*Ni)2(μ,.2‐P2)Cr(CO)5}2] (6). [(CO)5Cr}Cl2PPCl2Cr(CO)5}] (7) and [Cr(CO)5}2PCl (8). Comprehensive studies of the reaction pathway leading to formation of the cyclo‐P3 product 1a give strong indications that a sequence involving metal‐halogen exchange and stepwise P–P bond formation takes place, proceeding via [CO}5Cr}Cl2PPCl2Cr(CO)5}] (7) and the cyclo‐P3 precursor compond [Cp]Mo(CO)3}Cp'Mo(CO)2}2Cr(CO)5}(μ,.3:1:1−P3)] (9). The latter two complexes have been isolated and structurally characterized.