Reaction of Sulfur Dicyanide with IrCl(CO)(PR3)2 and the Structure of Chlorocyano(thiocyanato)-N-carbonylbis(triphenylphosphine)iridium(III), IrCl(CN)(NCS)(CO)(PPh3)2

James A. Ibers*, Diane S. Hamilton, W. H. Baddley

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Scopus citations


An X-ray structural determination and infrared studies of products of the reactions of sulfur dicyanide with IrCl(CO)L2 (L = PPh3, PMePh2) have shown that S(CN)2 acts as a pseudohalogen in its reactions with these substrates to form via trans addition the cyano-S-thiocyanato complexes IrCl(CN)(SCN)(CO)(L)2. Recrystallization of these compounds from dichlo-romethane-methanol is accompanied by isomerization to the N-thiocyanato complexes. The complex IrCl(CN)(NCS)(CO)-(PPh3)2 crystallizes with 1 molecule in space group Ci1-PT of the triclinic system in a reduced cell of dimensions a = 10. 141 (5), b = 11. 222 (5), c = 9. 381 (6) A; a = 112. 21 (5), β = 95. 02 (5), y = 64. 23 (4)°; λ(Cu Kα1) 1. 54056 A. The observed and calculated densities are 1. 57 (3) and 1. 62 g cm-3. Refinement of a model with CO disordered with trans Cl and CN disordered with the NC part of the trans NCS has resulted in a conventional R factor on F of 3. 2% for the 1238 counter data having I > 3σ(7). Because of the crystallographically imposed center of symmetry, and resultant disorder, bond distances and angles are not of high precision. Important bond distances include Ir-P = 2. 418 (3), Ir-Cl = 2. 37 (1), Ir-C(of CO) = 1. 84 (4), Ir-(C/N) = 1. 99 (1), and (C/N)-S = 1. 62 A. The complex is essentially octahedral, and the N-C-S linkage is linear.

Original languageEnglish (US)
Pages (from-to)229-232
Number of pages4
JournalInorganic chemistry
Issue number1
StatePublished - Jan 1 1973

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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