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The synthesis, x-ray crystal structure, and solution characterization of a bis(diphosphine)-bridged dirhodium(I) complex containing a Rh2P4 six-membered ring

Publication ,  Journal Article
Crumbliss, AL; Topping, RJ; Szewczyk, J; McPhail, AT; Quin, LD
Published in: Journal of the Chemical Society, Dalton Transactions
January 1, 1986

The preparation of [{Rh(cod)}2(μ-L1)2][BF4] 2 (1) from (CH2CMe=CH2P)2 (L1) and [Rh(cod)2]-BF4 (cod = cyclo-octa-1,5-diene) is described. The compound crystallizes in the monoclinic space group P21/c (C52h), with a = 9.650(1), b = 11.609(1), c = 21.884(3) Å, β = 117.07(1)°, and Z = 2. The structure was refined to R = 0.033 for 3 434 reflections. The solid-state structure shows two diphosphine ligands L1 bridging two rhodium(I) atoms to form a six-membered Rh2P4 ring in a chair conformation. Solution studies (1H and 13C-{1H} variable-temperature n.m.r. spectra) exhibit characteristics of a ring inversion equilibrium with ΔG271 = 14.0(0.2) kcal mol-1. Computer simulation of the 31P-{1H} n.m.r. spectrum is used to analyse the internuclear couplings of the AA′A″A‴XX′ pattern (A = 31P, X = 103Rh). The bridging diphosphine ligands exhibit a deshielding effect on the trans olefinic carbon atoms of cod in (1) which is in the range normally found for phosphine ligands.

Duke Scholars

Published In

Journal of the Chemical Society, Dalton Transactions

DOI

ISSN

1472-7773

Publication Date

January 1, 1986

Issue

9

Start / End Page

1895 / 1899

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0307 Theoretical and Computational Chemistry
  • 0302 Inorganic Chemistry
 

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Crumbliss, A. L., Topping, R. J., Szewczyk, J., McPhail, A. T., & Quin, L. D. (1986). The synthesis, x-ray crystal structure, and solution characterization of a bis(diphosphine)-bridged dirhodium(I) complex containing a Rh2P4 six-membered ring. Journal of the Chemical Society, Dalton Transactions, (9), 1895–1899. https://doi.org/10.1039/DT9860001895
Crumbliss, A. L., R. J. Topping, J. Szewczyk, A. T. McPhail, and L. D. Quin. “The synthesis, x-ray crystal structure, and solution characterization of a bis(diphosphine)-bridged dirhodium(I) complex containing a Rh2P4 six-membered ring.” Journal of the Chemical Society, Dalton Transactions, no. 9 (January 1, 1986): 1895–99. https://doi.org/10.1039/DT9860001895.
Crumbliss AL, Topping RJ, Szewczyk J, McPhail AT, Quin LD. The synthesis, x-ray crystal structure, and solution characterization of a bis(diphosphine)-bridged dirhodium(I) complex containing a Rh2P4 six-membered ring. Journal of the Chemical Society, Dalton Transactions. 1986 Jan 1;(9):1895–9.
Crumbliss, A. L., et al. “The synthesis, x-ray crystal structure, and solution characterization of a bis(diphosphine)-bridged dirhodium(I) complex containing a Rh2P4 six-membered ring.” Journal of the Chemical Society, Dalton Transactions, no. 9, Jan. 1986, pp. 1895–99. Scopus, doi:10.1039/DT9860001895.
Crumbliss AL, Topping RJ, Szewczyk J, McPhail AT, Quin LD. The synthesis, x-ray crystal structure, and solution characterization of a bis(diphosphine)-bridged dirhodium(I) complex containing a Rh2P4 six-membered ring. Journal of the Chemical Society, Dalton Transactions. 1986 Jan 1;(9):1895–1899.

Published In

Journal of the Chemical Society, Dalton Transactions

DOI

ISSN

1472-7773

Publication Date

January 1, 1986

Issue

9

Start / End Page

1895 / 1899

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0307 Theoretical and Computational Chemistry
  • 0302 Inorganic Chemistry