π-Bonded Disulfur. Structure of Disulfurbis (bis(diphenylphosphino) ethane) iridium (I) Chloride Acetonitrlle

Wesley D. Bonds; James A. Ibers

doi:10.1021/ja00765a026

π-Bonded Disulfur. Structure of Disulfurbis (bis(diphenylphosphino) ethane) iridium (I) Chloride Acetonitrlle

Wesley D. Bonds, James A. Ibers

Chemistry

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Abstract

The structure of disulfurbis(bis(diphenylphosphino)ethane)iridium(I) chlorideacetonitrile, [Ir(S₂)-((C₆H₅)₂PCH₂CH₂P(C₆H₅)₂)₂]Cl·CH₃CN, has been determined from three-dimensional X-ray data collected by counter methods. This compound crystallizes in space group D2d4-P421c of the tetragonal system with four formula weights per cell (a = 22.064 (9), c = 20.747 (9) A). The observed and calculated densities are 1.51 (2) and 1.486 g/cm3, respectively. Full-matrix least-squares refinement of the structure has yielded a final conventional R factor of 0.050 (on F) for the 3041 independent reflections with F² > 3tr(F²). The ions and solvate molecule occupy general positions in the cell. The [Ir(S₂)((C₆H₅)₂PCH₂CH₂P(C₆H₅)₂)₂]+ cation displays approximately trigonal-bipyramidal coordination and is nearly isostructural with the previously reported oxygen carriers, [M(O₂)((C₆H₅)₂-PCH₂CH₂P(C₆H))₂)₂]⁺= (M = Ir, Rh). The disulfur molecule is ir bonded at an equatorial site, with an average Ir-S distance of 2.41 (2) A. The four phosphorus atoms complete the coordination sphere at 2.33-2.37 A from the metal. While the S-S linkage of 2.066 (6) A is similar to that reported for octasulfur (2.060 (3) A), it is significantly longer than the 1.889-Å S-S bond in free disulfur. The Ir-S2 bonding is easily rationalized in terms of the π-bonding model previously advanced for the d8 oxygen carriers.

Original language	English (US)
Pages (from-to)	3413-3419
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	94
Issue number	10
DOIs	https://doi.org/10.1021/ja00765a026
State	Published - May 1 1972

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "π-Bonded Disulfur. Structure of Disulfurbis (bis(diphenylphosphino) ethane) iridium (I) Chloride Acetonitrlle",

abstract = "The structure of disulfurbis(bis(diphenylphosphino)ethane)iridium(I) chlorideacetonitrile, [Ir(S2)-((C6H5)2PCH2CH2P(C6H5)2)2]Cl·CH3CN, has been determined from three-dimensional X-ray data collected by counter methods. This compound crystallizes in space group D2d4-P421c of the tetragonal system with four formula weights per cell (a = 22.064 (9), c = 20.747 (9) A). The observed and calculated densities are 1.51 (2) and 1.486 g/cm3, respectively. Full-matrix least-squares refinement of the structure has yielded a final conventional R factor of 0.050 (on F) for the 3041 independent reflections with F2 > 3tr(F2). The ions and solvate molecule occupy general positions in the cell. The [Ir(S2)((C6H5)2PCH2CH2P(C6H5)2)2]+ cation displays approximately trigonal-bipyramidal coordination and is nearly isostructural with the previously reported oxygen carriers, [M(O2)((C6H5)2-PCH2CH2P(C6H))2)2]+= (M = Ir, Rh). The disulfur molecule is ir bonded at an equatorial site, with an average Ir-S distance of 2.41 (2) A. The four phosphorus atoms complete the coordination sphere at 2.33-2.37 A from the metal. While the S-S linkage of 2.066 (6) A is similar to that reported for octasulfur (2.060 (3) A), it is significantly longer than the 1.889-{\AA} S-S bond in free disulfur. The Ir-S2 bonding is easily rationalized in terms of the π-bonding model previously advanced for the d8 oxygen carriers.",

author = "Bonds, {Wesley D.} and Ibers, {James A.}",

year = "1972",

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doi = "10.1021/ja00765a026",

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T1 - π-Bonded Disulfur. Structure of Disulfurbis (bis(diphenylphosphino) ethane) iridium (I) Chloride Acetonitrlle

AU - Bonds, Wesley D.

AU - Ibers, James A.

PY - 1972/5/1

Y1 - 1972/5/1

N2 - The structure of disulfurbis(bis(diphenylphosphino)ethane)iridium(I) chlorideacetonitrile, [Ir(S2)-((C6H5)2PCH2CH2P(C6H5)2)2]Cl·CH3CN, has been determined from three-dimensional X-ray data collected by counter methods. This compound crystallizes in space group D2d4-P421c of the tetragonal system with four formula weights per cell (a = 22.064 (9), c = 20.747 (9) A). The observed and calculated densities are 1.51 (2) and 1.486 g/cm3, respectively. Full-matrix least-squares refinement of the structure has yielded a final conventional R factor of 0.050 (on F) for the 3041 independent reflections with F2 > 3tr(F2). The ions and solvate molecule occupy general positions in the cell. The [Ir(S2)((C6H5)2PCH2CH2P(C6H5)2)2]+ cation displays approximately trigonal-bipyramidal coordination and is nearly isostructural with the previously reported oxygen carriers, [M(O2)((C6H5)2-PCH2CH2P(C6H))2)2]+= (M = Ir, Rh). The disulfur molecule is ir bonded at an equatorial site, with an average Ir-S distance of 2.41 (2) A. The four phosphorus atoms complete the coordination sphere at 2.33-2.37 A from the metal. While the S-S linkage of 2.066 (6) A is similar to that reported for octasulfur (2.060 (3) A), it is significantly longer than the 1.889-Å S-S bond in free disulfur. The Ir-S2 bonding is easily rationalized in terms of the π-bonding model previously advanced for the d8 oxygen carriers.

AB - The structure of disulfurbis(bis(diphenylphosphino)ethane)iridium(I) chlorideacetonitrile, [Ir(S2)-((C6H5)2PCH2CH2P(C6H5)2)2]Cl·CH3CN, has been determined from three-dimensional X-ray data collected by counter methods. This compound crystallizes in space group D2d4-P421c of the tetragonal system with four formula weights per cell (a = 22.064 (9), c = 20.747 (9) A). The observed and calculated densities are 1.51 (2) and 1.486 g/cm3, respectively. Full-matrix least-squares refinement of the structure has yielded a final conventional R factor of 0.050 (on F) for the 3041 independent reflections with F2 > 3tr(F2). The ions and solvate molecule occupy general positions in the cell. The [Ir(S2)((C6H5)2PCH2CH2P(C6H5)2)2]+ cation displays approximately trigonal-bipyramidal coordination and is nearly isostructural with the previously reported oxygen carriers, [M(O2)((C6H5)2-PCH2CH2P(C6H))2)2]+= (M = Ir, Rh). The disulfur molecule is ir bonded at an equatorial site, with an average Ir-S distance of 2.41 (2) A. The four phosphorus atoms complete the coordination sphere at 2.33-2.37 A from the metal. While the S-S linkage of 2.066 (6) A is similar to that reported for octasulfur (2.060 (3) A), it is significantly longer than the 1.889-Å S-S bond in free disulfur. The Ir-S2 bonding is easily rationalized in terms of the π-bonding model previously advanced for the d8 oxygen carriers.

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π-Bonded Disulfur. Structure of Disulfurbis (bis(diphenylphosphino) ethane) iridium (I) Chloride Acetonitrlle

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