Metal-metal interactions in binuclear complexes. Structural characterization of isomers resulting from apparent internal oxidative addition of a platinum-chlorine bond to a rhodium(I) center

Alan L. Balch, Rosalvina R. Guimerans, John Linehan, Marilyn M. Olmstead, Douglas E. Oram

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Abstract

The face-to-face complex trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2, 1, isomerizes to trans-Rh-(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl upon heating in chloroform or upon treatment with a small amount of Ph2AsCH2PPh2. Metathesis of 1 with iodide produces trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI, and the bromo analogue has been prepared similarly. trans-Rh(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl·2CH2Cl2, 2, crystallizes in the monoclinic space group P21/c with a = 17.563 (4) Å, b = 14.995 (4) Å, c = 21.338 (4) Å, β = 105.90 (2)°, V = 5404 (2) Å3, and Z = 4, at 140 K. The structure was refined to a conventional R value of 0.051 using 6017 unique reflections and 334 parameters. trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI-CH2Cl 2·2CHCl3, 4, crystallizes in the orthorhombic space group Pbca with a = 17.808 (8) Å, b = 19.488 (8) Å, c = 35.228 (15) Å, V = 12225.6 (9) Å3, and Z = 8 at 140 K. The structure was refined to a conventional R value of 0.092 using 5001 unique data and 344 parameters. Both structures are similar with a six-coordinate rhodium atom (ligands: two As, CO, two Cl or two I, Pt) and a four-coordinate platinum (ligands two P, Rh, Cl or I) joined by a Pt-Rh bond (2.692 (1) Å in 2 and 2.737 (3) Å in 4). The carbonyl group in both complexes displays a subtle tilting toward the platinum atom. This results in a significant lowering (20-40 cm-1) of the carbonyl stretching frequency.

Original languageEnglish
Pages (from-to)1445-1451
Number of pages7
JournalOrganometallics
Volume4
Issue number8
Publication statusPublished - 1985

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Rhodium
Chlorine
Carbon Monoxide
Platinum
rhodium
Isomers
chlorine
platinum
isomers
Metals
metals
ligands
metathesis
interactions
chloroform
iodides
atoms
analogs
Ligands
Atoms

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Metal-metal interactions in binuclear complexes. Structural characterization of isomers resulting from apparent internal oxidative addition of a platinum-chlorine bond to a rhodium(I) center. / Balch, Alan L.; Guimerans, Rosalvina R.; Linehan, John; Olmstead, Marilyn M.; Oram, Douglas E.

In: Organometallics, Vol. 4, No. 8, 1985, p. 1445-1451.

Research output: Contribution to journalArticle

@article{25c57b2c8c7b4722a74c42119b768cd5,
title = "Metal-metal interactions in binuclear complexes. Structural characterization of isomers resulting from apparent internal oxidative addition of a platinum-chlorine bond to a rhodium(I) center",
abstract = "The face-to-face complex trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2, 1, isomerizes to trans-Rh-(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl upon heating in chloroform or upon treatment with a small amount of Ph2AsCH2PPh2. Metathesis of 1 with iodide produces trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI, and the bromo analogue has been prepared similarly. trans-Rh(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl·2CH2Cl2, 2, crystallizes in the monoclinic space group P21/c with a = 17.563 (4) {\AA}, b = 14.995 (4) {\AA}, c = 21.338 (4) {\AA}, β = 105.90 (2)°, V = 5404 (2) {\AA}3, and Z = 4, at 140 K. The structure was refined to a conventional R value of 0.051 using 6017 unique reflections and 334 parameters. trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI-CH2Cl 2·2CHCl3, 4, crystallizes in the orthorhombic space group Pbca with a = 17.808 (8) {\AA}, b = 19.488 (8) {\AA}, c = 35.228 (15) {\AA}, V = 12225.6 (9) {\AA}3, and Z = 8 at 140 K. The structure was refined to a conventional R value of 0.092 using 5001 unique data and 344 parameters. Both structures are similar with a six-coordinate rhodium atom (ligands: two As, CO, two Cl or two I, Pt) and a four-coordinate platinum (ligands two P, Rh, Cl or I) joined by a Pt-Rh bond (2.692 (1) {\AA} in 2 and 2.737 (3) {\AA} in 4). The carbonyl group in both complexes displays a subtle tilting toward the platinum atom. This results in a significant lowering (20-40 cm-1) of the carbonyl stretching frequency.",
author = "Balch, {Alan L.} and Guimerans, {Rosalvina R.} and John Linehan and Olmstead, {Marilyn M.} and Oram, {Douglas E.}",
year = "1985",
language = "English",
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journal = "Organometallics",
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T1 - Metal-metal interactions in binuclear complexes. Structural characterization of isomers resulting from apparent internal oxidative addition of a platinum-chlorine bond to a rhodium(I) center

AU - Balch, Alan L.

AU - Guimerans, Rosalvina R.

AU - Linehan, John

AU - Olmstead, Marilyn M.

AU - Oram, Douglas E.

PY - 1985

Y1 - 1985

N2 - The face-to-face complex trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2, 1, isomerizes to trans-Rh-(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl upon heating in chloroform or upon treatment with a small amount of Ph2AsCH2PPh2. Metathesis of 1 with iodide produces trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI, and the bromo analogue has been prepared similarly. trans-Rh(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl·2CH2Cl2, 2, crystallizes in the monoclinic space group P21/c with a = 17.563 (4) Å, b = 14.995 (4) Å, c = 21.338 (4) Å, β = 105.90 (2)°, V = 5404 (2) Å3, and Z = 4, at 140 K. The structure was refined to a conventional R value of 0.051 using 6017 unique reflections and 334 parameters. trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI-CH2Cl 2·2CHCl3, 4, crystallizes in the orthorhombic space group Pbca with a = 17.808 (8) Å, b = 19.488 (8) Å, c = 35.228 (15) Å, V = 12225.6 (9) Å3, and Z = 8 at 140 K. The structure was refined to a conventional R value of 0.092 using 5001 unique data and 344 parameters. Both structures are similar with a six-coordinate rhodium atom (ligands: two As, CO, two Cl or two I, Pt) and a four-coordinate platinum (ligands two P, Rh, Cl or I) joined by a Pt-Rh bond (2.692 (1) Å in 2 and 2.737 (3) Å in 4). The carbonyl group in both complexes displays a subtle tilting toward the platinum atom. This results in a significant lowering (20-40 cm-1) of the carbonyl stretching frequency.

AB - The face-to-face complex trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2, 1, isomerizes to trans-Rh-(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl upon heating in chloroform or upon treatment with a small amount of Ph2AsCH2PPh2. Metathesis of 1 with iodide produces trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI, and the bromo analogue has been prepared similarly. trans-Rh(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl·2CH2Cl2, 2, crystallizes in the monoclinic space group P21/c with a = 17.563 (4) Å, b = 14.995 (4) Å, c = 21.338 (4) Å, β = 105.90 (2)°, V = 5404 (2) Å3, and Z = 4, at 140 K. The structure was refined to a conventional R value of 0.051 using 6017 unique reflections and 334 parameters. trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI-CH2Cl 2·2CHCl3, 4, crystallizes in the orthorhombic space group Pbca with a = 17.808 (8) Å, b = 19.488 (8) Å, c = 35.228 (15) Å, V = 12225.6 (9) Å3, and Z = 8 at 140 K. The structure was refined to a conventional R value of 0.092 using 5001 unique data and 344 parameters. Both structures are similar with a six-coordinate rhodium atom (ligands: two As, CO, two Cl or two I, Pt) and a four-coordinate platinum (ligands two P, Rh, Cl or I) joined by a Pt-Rh bond (2.692 (1) Å in 2 and 2.737 (3) Å in 4). The carbonyl group in both complexes displays a subtle tilting toward the platinum atom. This results in a significant lowering (20-40 cm-1) of the carbonyl stretching frequency.

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