Issue 10, 1991

Synthesis and reactivity of bis(diphenylphosphine) methane(dppm)-bridged Pd–Mo and Pd–W complexes. Crystal structure of [Pd(µ-CO)(µ-dppm)2Mo(cp)(CO)][PF6](cp =η5-C5H5)

Abstract

Reactions of [PdCl2(dppm-PP′)](dppm = Ph2PCH2PPh2) with Na[M′(CO)]·2dme [M′= Mo(cp)(CO)2 or W(cp)(CO)2; cp =η5-C5H5, dme = 1,2-dimethoxyethane] gave trinuclear clusters of type [PdM2(cp)(CO)5(µ-dppm)](M = Mo, 1; or W, 2). Treatment of 1 or 2 with 1 equivalent of dppm resulted in heterolytic metal–metal bond cleavage and afforded dinuclear cationic complexes [[graphic omitted](cp)(CO)][M(cp)(CO)3](M = Mo, 3a; or W, 4a). The structure of the benzene solvate the PF6 salt of 3, i.e.3b, was established by a single-crystal X-ray analysis: space group P2/c, a= 23.923(6), b= 11.040(3), c= 24.012(6)Å, β= 90.79(2)°, R= 0.053 for 7361 reflections. The (cp)MoP(1)P(3)(CO)2 fragment is square pyramidal, with the cp at the apex, and the co-ordination at Mo may be viewed as of the 3:4:1 type when including the bonding to Pd [Pd–Mo] 2.799(1)Å]. The unusual geometry around Pd is trigonal planar when considering its bonds to P(2), P(4) and Mo. The bridging carbonyl C(56)O(1) completes its co-ordination sphere. Complexes 3b and 4b were also prepared from [Pd(dppm-PP2)2][BF4]2 and 2 equivalents of Na[M′(CO)]·2dme [M′= Mo(cp)(CO)2 or W(cp)(CO)2]. Their characteristic 31P-{1H} NMR spectra are respectively of the AA′XX′ and AA′BB′ types. Reactivity studies were performed and the new bimetallic complex [(OC)2(cp)[graphic omitted]tCl(PPh3)]8 is also described.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1991, 2685-2692

Synthesis and reactivity of bis(diphenylphosphine) methane(dppm)-bridged Pd–Mo and Pd–W complexes. Crystal structure of [Pd(µ-CO)(µ-dppm)2Mo(cp)(CO)][PF6](cp =η5-C5H5)

P. Braunstein, B. Oswald, A. DeCian and J. Fischer, J. Chem. Soc., Dalton Trans., 1991, 2685 DOI: 10.1039/DT9910002685

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements