Preparation and structure of mono- and binuclear complexes of (diphenylarsino)(diphenylphosphino)methane including the x-ray crystal structure of trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2

Alan L. Balch, Rosalvina R. Guimerans, John Linehan, Fred E. Wood

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Abstract

The reactions of (diphenylarsino)(diphenylphosphino)methane with (1,5-COD)PtX2 (1,5-COD = 1,5-cyclooctadiene; X = Cl, Br, I) or with Rh2(CO)4(μ-Cl)2 to yield Pt(dapm)X2 (chelating dapm), Pt(dapm)2X2, or trans-Rh(dapm)2(CO)Cl (monodentate dapm) are reported. In solution Pt(dapm)2X2 can ionize to form [Pt(damp)2X]X or [Pt(dapm)2]X2. The degree of ionization depends on X and on the solvent. trans-Rh(dapm)2(CO)Cl reacts with Rh2(CO)4(μ-Cl)2 to yield the face-to-face dimer Rh2(μ-dapm)2(CO)2Cl2 as a mixture of head-to-head (P trans to P) and head-to-tail (P trans to As) isomers. Pt(dapm)2Cl2 reacts with Pt(dibenzylideneacetone)2 to form head-to-head and head-to-tail isomers of Pt2(μ-dapm)2Cl2. These react with carbon monoxide to form Pt2(μ-dapm)2(μ-CO)Cl2. Rh2(CO)4(μ-Cl)2 reacts with Pt(dapm)2Cl2 to form trans-Rh(CO)Cl(μ-dapm)2-cis-PtCl2. This orange complex crystallizes in the space group P21/c (No. 14) with a = 18.760 (3) Å, b = 11.610 (3) Å, c = 22.954 (6) Å, β = 92.81 (2)°, and Z = 4 at 140 K. The structure was refined to a conventional R value of 0.038 by using 6415 significant reflections and 572 parameters. The structure consists of face-to-face planar Rh(CO)ClAs2 and PtP2Cl2 units. The nonbonded Pt⋯Rh distance is 3.043 (1) Å.

Original languageEnglish
Pages (from-to)2021-2026
Number of pages6
JournalInorganic Chemistry
Volume24
Issue number13
Publication statusPublished - 1985

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crack opening displacement
Methane
Carbon Monoxide
methane
isomers
Crystal structure
X rays
preparation
crystal structure
carbon monoxide
x rays
dimers
ionization
Isomers
Chelation
Dimers
Ionization

ASJC Scopus subject areas

  • Inorganic Chemistry

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Preparation and structure of mono- and binuclear complexes of (diphenylarsino)(diphenylphosphino)methane including the x-ray crystal structure of trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2 . / Balch, Alan L.; Guimerans, Rosalvina R.; Linehan, John; Wood, Fred E.

In: Inorganic Chemistry, Vol. 24, No. 13, 1985, p. 2021-2026.

Research output: Contribution to journalArticle

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title = "Preparation and structure of mono- and binuclear complexes of (diphenylarsino)(diphenylphosphino)methane including the x-ray crystal structure of trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2",
abstract = "The reactions of (diphenylarsino)(diphenylphosphino)methane with (1,5-COD)PtX2 (1,5-COD = 1,5-cyclooctadiene; X = Cl, Br, I) or with Rh2(CO)4(μ-Cl)2 to yield Pt(dapm)X2 (chelating dapm), Pt(dapm)2X2, or trans-Rh(dapm)2(CO)Cl (monodentate dapm) are reported. In solution Pt(dapm)2X2 can ionize to form [Pt(damp)2X]X or [Pt(dapm)2]X2. The degree of ionization depends on X and on the solvent. trans-Rh(dapm)2(CO)Cl reacts with Rh2(CO)4(μ-Cl)2 to yield the face-to-face dimer Rh2(μ-dapm)2(CO)2Cl2 as a mixture of head-to-head (P trans to P) and head-to-tail (P trans to As) isomers. Pt(dapm)2Cl2 reacts with Pt(dibenzylideneacetone)2 to form head-to-head and head-to-tail isomers of Pt2(μ-dapm)2Cl2. These react with carbon monoxide to form Pt2(μ-dapm)2(μ-CO)Cl2. Rh2(CO)4(μ-Cl)2 reacts with Pt(dapm)2Cl2 to form trans-Rh(CO)Cl(μ-dapm)2-cis-PtCl2. This orange complex crystallizes in the space group P21/c (No. 14) with a = 18.760 (3) {\AA}, b = 11.610 (3) {\AA}, c = 22.954 (6) {\AA}, β = 92.81 (2)°, and Z = 4 at 140 K. The structure was refined to a conventional R value of 0.038 by using 6415 significant reflections and 572 parameters. The structure consists of face-to-face planar Rh(CO)ClAs2 and PtP2Cl2 units. The nonbonded Pt⋯Rh distance is 3.043 (1) {\AA}.",
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T1 - Preparation and structure of mono- and binuclear complexes of (diphenylarsino)(diphenylphosphino)methane including the x-ray crystal structure of trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2

AU - Balch, Alan L.

AU - Guimerans, Rosalvina R.

AU - Linehan, John

AU - Wood, Fred E.

PY - 1985

Y1 - 1985

N2 - The reactions of (diphenylarsino)(diphenylphosphino)methane with (1,5-COD)PtX2 (1,5-COD = 1,5-cyclooctadiene; X = Cl, Br, I) or with Rh2(CO)4(μ-Cl)2 to yield Pt(dapm)X2 (chelating dapm), Pt(dapm)2X2, or trans-Rh(dapm)2(CO)Cl (monodentate dapm) are reported. In solution Pt(dapm)2X2 can ionize to form [Pt(damp)2X]X or [Pt(dapm)2]X2. The degree of ionization depends on X and on the solvent. trans-Rh(dapm)2(CO)Cl reacts with Rh2(CO)4(μ-Cl)2 to yield the face-to-face dimer Rh2(μ-dapm)2(CO)2Cl2 as a mixture of head-to-head (P trans to P) and head-to-tail (P trans to As) isomers. Pt(dapm)2Cl2 reacts with Pt(dibenzylideneacetone)2 to form head-to-head and head-to-tail isomers of Pt2(μ-dapm)2Cl2. These react with carbon monoxide to form Pt2(μ-dapm)2(μ-CO)Cl2. Rh2(CO)4(μ-Cl)2 reacts with Pt(dapm)2Cl2 to form trans-Rh(CO)Cl(μ-dapm)2-cis-PtCl2. This orange complex crystallizes in the space group P21/c (No. 14) with a = 18.760 (3) Å, b = 11.610 (3) Å, c = 22.954 (6) Å, β = 92.81 (2)°, and Z = 4 at 140 K. The structure was refined to a conventional R value of 0.038 by using 6415 significant reflections and 572 parameters. The structure consists of face-to-face planar Rh(CO)ClAs2 and PtP2Cl2 units. The nonbonded Pt⋯Rh distance is 3.043 (1) Å.

AB - The reactions of (diphenylarsino)(diphenylphosphino)methane with (1,5-COD)PtX2 (1,5-COD = 1,5-cyclooctadiene; X = Cl, Br, I) or with Rh2(CO)4(μ-Cl)2 to yield Pt(dapm)X2 (chelating dapm), Pt(dapm)2X2, or trans-Rh(dapm)2(CO)Cl (monodentate dapm) are reported. In solution Pt(dapm)2X2 can ionize to form [Pt(damp)2X]X or [Pt(dapm)2]X2. The degree of ionization depends on X and on the solvent. trans-Rh(dapm)2(CO)Cl reacts with Rh2(CO)4(μ-Cl)2 to yield the face-to-face dimer Rh2(μ-dapm)2(CO)2Cl2 as a mixture of head-to-head (P trans to P) and head-to-tail (P trans to As) isomers. Pt(dapm)2Cl2 reacts with Pt(dibenzylideneacetone)2 to form head-to-head and head-to-tail isomers of Pt2(μ-dapm)2Cl2. These react with carbon monoxide to form Pt2(μ-dapm)2(μ-CO)Cl2. Rh2(CO)4(μ-Cl)2 reacts with Pt(dapm)2Cl2 to form trans-Rh(CO)Cl(μ-dapm)2-cis-PtCl2. This orange complex crystallizes in the space group P21/c (No. 14) with a = 18.760 (3) Å, b = 11.610 (3) Å, c = 22.954 (6) Å, β = 92.81 (2)°, and Z = 4 at 140 K. The structure was refined to a conventional R value of 0.038 by using 6415 significant reflections and 572 parameters. The structure consists of face-to-face planar Rh(CO)ClAs2 and PtP2Cl2 units. The nonbonded Pt⋯Rh distance is 3.043 (1) Å.

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M3 - Article

VL - 24

SP - 2021

EP - 2026

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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