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

doi:10.1021/ic50119a050

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

Chemistry

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

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 C_i¹-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 language	English (US)
Pages (from-to)	229-232
Number of pages	4
Journal	Inorganic chemistry
Volume	12
Issue number	1
DOIs	https://doi.org/10.1021/ic50119a050
State	Published - Jan 1 1973

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{7c3a081fd0fd4462b3c26573c4a04651,

title = "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",

abstract = "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.",

author = "Ibers, {James A.} and Hamilton, {Diane S.} and Baddley, {W. H.}",

year = "1973",

month = jan,

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doi = "10.1021/ic50119a050",

language = "English (US)",

volume = "12",

pages = "229--232",

journal = "Inorganic chemistry",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - 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

AU - Ibers, James A.

AU - Hamilton, Diane S.

AU - Baddley, W. H.

PY - 1973/1/1

Y1 - 1973/1/1

N2 - 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.

AB - 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.

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U2 - 10.1021/ic50119a050

DO - 10.1021/ic50119a050

M3 - Article

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SN - 0020-1669

VL - 12

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JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 1

ER -

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

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