Multiple routes to the formation of a phosphine-bridged trirhodium dihydride cation, [Rh3{μ-(Ph2PCH2)2PPh} 2(H)2(μ-Cl)2(CO)2]+

Alan L. Balch, John Linehan, Marilyn M. Olmstead

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Red-orange [Rh3(μ-dpmp)2(H)2(μ-Cl) 2(CO)2][BPh4] (dpmp is bis((diphenylphosphino)methyl)phenylphosphine) is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)2(μ-Cl)Cl][BPh 4] or [Rh3(μ-dpmp)2(μ-CO)(CO)(μ-Cl)Cl][BPh4] with dihydrogen, by the reaction of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous formaldehyde, paraformaldehyde, or acetaldehyde, or by treatment of [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] with dihydrogen. Deep green [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous hydrochloric acid or hydrogen chloride vapor. Spectroscopic data characterizing these complexes are reported. [Rh3(μ-dpmp)2(H)2(CO) 2(μ-Cl)2][BPh4]·3CH 2Cl2 crystallizes in the space group P21/n (No. 14) with a = 14.498 (2) Å, b = 22.077 (3) Å, c = 28.353 (3) Å, β = 99.86 (1)°, and Z = 4 at 130 K, R = 0.049, Rw = 0.054 for 12079 reflections with I > 3σ(I) and 558 parameters. The complex consists of two chloro-bridged A-frame units linked side-by-side through the central rhodium. The hydrides, which were well-behaved on refinement, are primarily localized on the central rhodium; Rh(2)-H distances are 1.48 (7) and 1.55 (7) Å. Structural and 1H NMR spectroscopic evidence suggests a semibridging interaction between these hydrides and the terminal Rh(CO)Cl(P)2 units.

Original languageEnglish
Pages (from-to)3937-3942
Number of pages6
JournalInorganic Chemistry
Issue number22
Publication statusPublished - 1986


ASJC Scopus subject areas

  • Inorganic Chemistry

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