Crystal and Molecular Structure of Dinitrosylbis(triphenylphosphine)rhodium Perchlorate, [Rh(NO)2(P(C6H5)3)2][ClO4]

James A. Kaduk; James A. Ibers

doi:10.1021/ic50154a042

Crystal and Molecular Structure of Dinitrosylbis(triphenylphosphine)rhodium Perchlorate, [Rh(NO)₂(P(C₆H₅)₃)₂][ClO₄]

James A. Kaduk, James A. Ibers

Chemistry

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Abstract

The structure of dinitrosylbis(triphenylphosphine)rhodium perchlorate, [Rh(NO)₂(P(C₆H₅)₃)₂] [CIO₄], has been determined from three-dimensional X-ray data collected by counter methods. The compound crystallizes in the space group C2/c of the monoclinic system with four molecules in a unit cell of dimensions a = 17.134 (4) Å, b = 12.327 (3) Å, c = 17.166 (4) Å, and β = 108.17 (2)°. The observed and calculated densities are 1.55 (3) and 1.52 g cm^-3, respectively. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.061 for the 4649 independent reflections having F_o²> 3σ (F_o²). The crystal structure consists of well-separated, discrete, monomeric ions. The coordination geometry around the rhodium atom is best described as intermediate between tetrahedral and square planar; N-Rh-N = 157.5 (3) and P-Rh-P = 115.88(5)°. The Rh-N-O angle is 158.9 (4)°. The dihedral angle between the N-Rh-N and P-Rh-P planes is 86.0 (1)°, The structure is compared with those of other isoelectronic M(NO)₂(PPh₃)₂ complexes, and trends in structure and activity as catalysts for the reaction 2NO + CO ⟶ N₂O + CO₂ are correlated.

Original language	English (US)
Pages (from-to)	3070-3073
Number of pages	4
Journal	Inorganic chemistry
Volume	14
Issue number	12
DOIs	https://doi.org/10.1021/ic50154a042
State	Published - Dec 1 1975

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Crystal and Molecular Structure of Dinitrosylbis(triphenylphosphine)rhodium Perchlorate, [Rh(NO)2(P(C6H5)3)2][ClO4]",

abstract = "The structure of dinitrosylbis(triphenylphosphine)rhodium perchlorate, [Rh(NO)2(P(C6H5)3)2] [CIO4], has been determined from three-dimensional X-ray data collected by counter methods. The compound crystallizes in the space group C2/c of the monoclinic system with four molecules in a unit cell of dimensions a = 17.134 (4) {\AA}, b = 12.327 (3) {\AA}, c = 17.166 (4) {\AA}, and β = 108.17 (2)°. The observed and calculated densities are 1.55 (3) and 1.52 g cm-3, respectively. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.061 for the 4649 independent reflections having Fo2> 3σ (Fo2). The crystal structure consists of well-separated, discrete, monomeric ions. The coordination geometry around the rhodium atom is best described as intermediate between tetrahedral and square planar; N-Rh-N = 157.5 (3) and P-Rh-P = 115.88(5)°. The Rh-N-O angle is 158.9 (4)°. The dihedral angle between the N-Rh-N and P-Rh-P planes is 86.0 (1)°, The structure is compared with those of other isoelectronic M(NO)2(PPh3)2 complexes, and trends in structure and activity as catalysts for the reaction 2NO + CO ⟶ N2O + CO2 are correlated.",

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T1 - Crystal and Molecular Structure of Dinitrosylbis(triphenylphosphine)rhodium Perchlorate, [Rh(NO)2(P(C6H5)3)2][ClO4]

AU - Kaduk, James A.

AU - Ibers, James A.

PY - 1975/12/1

Y1 - 1975/12/1

N2 - The structure of dinitrosylbis(triphenylphosphine)rhodium perchlorate, [Rh(NO)2(P(C6H5)3)2] [CIO4], has been determined from three-dimensional X-ray data collected by counter methods. The compound crystallizes in the space group C2/c of the monoclinic system with four molecules in a unit cell of dimensions a = 17.134 (4) Å, b = 12.327 (3) Å, c = 17.166 (4) Å, and β = 108.17 (2)°. The observed and calculated densities are 1.55 (3) and 1.52 g cm-3, respectively. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.061 for the 4649 independent reflections having Fo2> 3σ (Fo2). The crystal structure consists of well-separated, discrete, monomeric ions. The coordination geometry around the rhodium atom is best described as intermediate between tetrahedral and square planar; N-Rh-N = 157.5 (3) and P-Rh-P = 115.88(5)°. The Rh-N-O angle is 158.9 (4)°. The dihedral angle between the N-Rh-N and P-Rh-P planes is 86.0 (1)°, The structure is compared with those of other isoelectronic M(NO)2(PPh3)2 complexes, and trends in structure and activity as catalysts for the reaction 2NO + CO ⟶ N2O + CO2 are correlated.

AB - The structure of dinitrosylbis(triphenylphosphine)rhodium perchlorate, [Rh(NO)2(P(C6H5)3)2] [CIO4], has been determined from three-dimensional X-ray data collected by counter methods. The compound crystallizes in the space group C2/c of the monoclinic system with four molecules in a unit cell of dimensions a = 17.134 (4) Å, b = 12.327 (3) Å, c = 17.166 (4) Å, and β = 108.17 (2)°. The observed and calculated densities are 1.55 (3) and 1.52 g cm-3, respectively. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.061 for the 4649 independent reflections having Fo2> 3σ (Fo2). The crystal structure consists of well-separated, discrete, monomeric ions. The coordination geometry around the rhodium atom is best described as intermediate between tetrahedral and square planar; N-Rh-N = 157.5 (3) and P-Rh-P = 115.88(5)°. The Rh-N-O angle is 158.9 (4)°. The dihedral angle between the N-Rh-N and P-Rh-P planes is 86.0 (1)°, The structure is compared with those of other isoelectronic M(NO)2(PPh3)2 complexes, and trends in structure and activity as catalysts for the reaction 2NO + CO ⟶ N2O + CO2 are correlated.

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Crystal and Molecular Structure of Dinitrosylbis(triphenylphosphine)rhodium Perchlorate, [Rh(NO)₂(P(C₆H₅)₃)₂][ClO₄]

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