THE REACTION OF P-4 WITH [CP'MO(CO)(3)](2) (CP' = ETA(5)-C(5)H(4)TBU)- THE STRUCTURE OF [CP'MO(CO)(2)[(ETA(3)-P-4)(CR(CO)(5))(4)(H)]]

The photochemical reaction of [Cp'Mo(CO)(3)](2) (Cp' = eta(5)-C(5)H(4) tBu) with white phosphorus in the presence of [Cr(CO)(5)thf] leads to the P-n ligand complexes [Cr(CO)(4)[(eta(4)-P-4){Cr(CO)(5)}(4)]] (1), [Cp'Mo(CO)(2)[(eta(3)-P-4){Cr(CO)(5))(4)(H)]] (2) and [{Cp'Mo(CO)(2)}( 2)[(mu, eta(2)-P-2){Cr(CO)(5)}(2)]] (3) The products were characterize d by NMR, IR and partially by X-ray structure analysis. The reaction p roceeds via a P-P bond cleavage leading to the bent cyclo-P-4 complex (CO)(2)[(eta(3)-P-4){Cr(CO)(5)}(4)(Cp'Mo(CO)(3)}]] (2a), which hydroly sis during the chromatographic work-up to give the more stable-compoun d 2. Furthermore, a P-3/P-1 fragmentation of 2a occurs to form the pho sphido complex intermediate [Cp'(CO)(2)Mo=P-->Cr(CO)(5)]. The latter d imerises resulting in the formation of the tetrahedral compound 3, con taining a Mo2P2 moiety. (C) 1998 Elsevier Science Ltd. All rights rese rved.