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Structure and properties of cis-bis(dicyclohexylphosphine)dihalogeno-nickel(II) complexes

Publication ,  Journal Article
Palmer, RA; Giles, HF; Whitcomb, DR
Published in: Journal of the Chemical Society, Dalton Transactions
December 1, 1978

Dicyclohexylphosphine and tetracyclohexyldiphosphane both react with anhydrous nickel(II) chloride and bromide to form the same type of complex in either case, namely cis-[NiX2{P(C6H11)2H}2] (X = Cl or Br). This has been confirmed in the solid state by X-ray diffraction and in solution by 1H and 31P n.m.r. spectroscopy. Other spectro-scopic data, as well as melting points, molecular weights, and elemental analyses, are also compatible with this conclusion. Evidence for a trans isomer of the bromide in solution is also observed. No evidence for the formation of a three-membered chelate ring in the reactions with the diphosphane could be detected. The 31P chemical shifts in CH2Cl2, are 36.4 (20 °C, 0.2 mol dm-3) and -46.1 and -30.5 p.p.m. (0 °C, 0.2 mol dm-3) for cis-[NiCl2{P(C6H11)2H}2], cis-[NiBr2{P(C6H11)2H}2], and trans-[NiBr2{P(C6H11)2H} 2] respectively, relative to 85% H3PO4. The complexes exhibit strong P-H coupling due to the secondary phosphine proton. X-Ray diffraction shows that cis-[NiCl2{P(C6H11)2H}2] crystallizes in the tetragonal space group /41/a (No. 88) with a = 20.69(1) and b = 25.15(2) Å, and Z = 16. The structure was solved, using Weissenberg methods and the heavy-atom technique from 1400 independent reflections using Cu-Kα radiation, to R′ 0.118. The nickel atom is 0.05 Å from the plane formed by the chlorine and phosphorus atoms. The average Ni-Cl distance IS 2.20(1) Å and the average Ni - P distance is 2.15(l) Å.

Duke Scholars

Published In

Journal of the Chemical Society, Dalton Transactions

DOI

ISSN

1472-7773

Publication Date

December 1, 1978

Issue

12

Start / End Page

1671 / 1677

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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Palmer, R. A., Giles, H. F., & Whitcomb, D. R. (1978). Structure and properties of cis-bis(dicyclohexylphosphine)dihalogeno-nickel(II) complexes. Journal of the Chemical Society, Dalton Transactions, (12), 1671–1677. https://doi.org/10.1039/DT9780001671
Palmer, R. A., H. F. Giles, and D. R. Whitcomb. “Structure and properties of cis-bis(dicyclohexylphosphine)dihalogeno-nickel(II) complexes.” Journal of the Chemical Society, Dalton Transactions, no. 12 (December 1, 1978): 1671–77. https://doi.org/10.1039/DT9780001671.
Palmer RA, Giles HF, Whitcomb DR. Structure and properties of cis-bis(dicyclohexylphosphine)dihalogeno-nickel(II) complexes. Journal of the Chemical Society, Dalton Transactions. 1978 Dec 1;(12):1671–7.
Palmer, R. A., et al. “Structure and properties of cis-bis(dicyclohexylphosphine)dihalogeno-nickel(II) complexes.” Journal of the Chemical Society, Dalton Transactions, no. 12, Dec. 1978, pp. 1671–77. Scopus, doi:10.1039/DT9780001671.
Palmer RA, Giles HF, Whitcomb DR. Structure and properties of cis-bis(dicyclohexylphosphine)dihalogeno-nickel(II) complexes. Journal of the Chemical Society, Dalton Transactions. 1978 Dec 1;(12):1671–1677.

Published In

Journal of the Chemical Society, Dalton Transactions

DOI

ISSN

1472-7773

Publication Date

December 1, 1978

Issue

12

Start / End Page

1671 / 1677

Related Subject Headings

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