139732-82-4Relevant articles and documents
Reactions of perfluoromethyl-substituted cyclopolyphosphines with zerovalent group 10 metal complexes. Crystal and molecular structure of a complex with a coordinated diphosphene, [Pd(η2-CF3P=PCF3)(PPh3) 2]
Phillips, Ian G.,Ball, Richard G.,Cavell, Ronald G.
, p. 1633 - 1641 (2008/10/08)
Reactions of trifluoromethyl-substituted cyclopolyphosphines (CF3P)4 and (CF3P)5 with zerovalent Pt, Pd, and Ni complexes gave a variety of products under different conditions. The most definitive reactions were those in which (CF3P)4 reacted with the zerovalent metal complexes under refluxing conditions in benzene to give η2-CF3PPCF3 complexes of the formula L2M(CF3PPCF3). The crystal and molecular structure of (Ph3P)2Pd(η2-CF3PPCF 3) (monoclinic P21/n, Z = 4, a = 11.200 (2) A?, b = 19.441 (3) A?, c = 17.502 (3) A?, β= 101.71 (1)°, R1 = 0.048, R2 = 0.062) showed clearly the η2 adduct in the E configuration. The P=P bond length of 2.121 A? is consistent with a coordinated diphosphene as formulated. The CF3PPCF3 group can be transferred to different metals (e.g. Pt) by simple metathetical exchange. The various coordinated and ring-opened intermediates formed via initial 1,3-coordination of the cyclic polyphosphines both (CF3P)4 and (CF3P)5 and subsequent ring opening were identified by NMR spectroscopy, and some aspects of the mechanism of formation of the intermediates and the final η2 adduct are discussed.
