Extension of the Karplus relationship to vicinal coupling within the P–Ru–S–H moiety of the H₂S complexes cis-RuX₂(P–N)(PPh₃)(SH₂) {X = Cl, Br; P–N = [o-(N,N-dimethylamino)phenyl]diphenylphosphine}

Abstract

The Ru(II)–H₂S complexes cis-RuX₂(P–N)(PPh₃)(SH₂) {X = Cl, Br; P–N = [o-(N,N-dimethylamino)phenyl]diphenylphosphine} are characterised crystallographically and by ³¹P{¹H}, ¹H and ¹H{³¹P} NMR spectroscopies; the ¹H NMR spectra at –50 °C show three-bond coupling of only one H-atom of the coordinated H₂S to the P-atom of the P–N ligand, and this represents an extension of the Karplus relationship to vicinal coupling within a P–Ru–S–H system.

References

1. B. R. James, Pure Appl. Chem., 1997, 69, 2213 and references therein T. Y. H. Wong, B. R. James, P. C. Wong and K. A. R. Mitchell, J. Mol. Catal. A: Chem., 1999, 139, 159 and references therein.
2. D. C. Mudalige, E. S. Ma, S. J. Rettig, B. R. James and W. R. Cullen, Inorg. Chem., 1997, 36, 5426.
3. D. C. Mudalige, S. J. Rettig, B. R. James and W. R. Cullen, J. Chem. Soc., Chem. Commun., 1993, 830.
4. T. H. Edwards, N. K. Moncur and L. E. Snyder, J. Chem. Phys., 1967, 46, 2139; I. G. Csizmadia, in The Chemistry of the Thiol Group, Part I, ed. S. Patai, John Wiley & Sons, Toronto, 1974, p. 7.
5. K. Osakada, T. Yamamoto and A. Yamamoto, Inorg. Chim. Acta, 1985, 105, L9.
6. R. Angelici, Acc. Chem. Res., 1988, 21, 387.
7. M. Karplus, J. Chem. Phys., 1959, 30, 11; J. Am. Chem. Soc., 1963, 85, 2870.
8. W. G. Bentrude and W. N. Setzer, in Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis, ed. J. G. Verkade and L. D. Quin, VCH Publishers, Inc., Deerfield Beach, FL, 1987, p. 365.