Low-temperature neutron diffraction study of HMn2Re(CO)14 and studies of a metal metal exchange equilibrium that converts HMn2Re(CO)14 into HMnRe2(CO)14

R Morris Bullock, Lee Brammer, Arthur J. Schultz, Alberto Albinati, Thomas F. Koetzle

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Abstract

The crystal and molecular structure of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5, prepared from reaction of Mn2-(CO)91-tolualdehyde) with HRe(CO)5, has been determined from neutron diffraction measurements at 15 K: unit-cell constants, a = 9.145 (1) Å, b = 15.557 (3) Å, c = 14.040 (3) Å, β = 106.60 (2)°, monoclinic, space group P21/n, Z = 4, V = 1914.2 (6) Å3, R(F2) = 0.110 for 4859 reflections with F0 2 ≥ 3σ(F0 2) and (sin θ/λ)max = 1.054 Å-1. The Re-H distance (1.827 (4) Å) is longer than the Mn-H distance (1.719 (5) Å). Spectroscopic and crystallographic data indicate that a small amount (∼9%) of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 has cocrystallized with the major component. Further evidence for the identity of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 comes from an independent synthesis by a known route. A mechanism is proposed that accounts for the formation of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 from the reaction of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 with HRe(CO)5. The equilibrium constant for the metal-metal exchange equilibrium, (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 + HRe(CO)5 = (CO)5Re(μ-H)Mn(CO)4Re(CO)5 + HMn(CO)5, has been determined; Keq = 1.00 ± 0.05 at 22 °C in C6D6.

Original languageEnglish
Pages (from-to)5125-5130
Number of pages6
JournalJournal of the American Chemical Society
Volume114
Issue number13
Publication statusPublished - 1992

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Neutron Diffraction
Carbon Monoxide
Neutron diffraction
Metals
Temperature
Equilibrium constants
Molecular structure
Crystal structure

ASJC Scopus subject areas

  • Chemistry(all)

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Low-temperature neutron diffraction study of HMn2Re(CO)14 and studies of a metal metal exchange equilibrium that converts HMn2Re(CO)14 into HMnRe2(CO)14 . / Bullock, R Morris; Brammer, Lee; Schultz, Arthur J.; Albinati, Alberto; Koetzle, Thomas F.

In: Journal of the American Chemical Society, Vol. 114, No. 13, 1992, p. 5125-5130.

Research output: Contribution to journalArticle

@article{03b1bde152f34717be27dba629e026df,
title = "Low-temperature neutron diffraction study of HMn2Re(CO)14 and studies of a metal metal exchange equilibrium that converts HMn2Re(CO)14 into HMnRe2(CO)14",
abstract = "The crystal and molecular structure of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5, prepared from reaction of Mn2-(CO)9(η1-tolualdehyde) with HRe(CO)5, has been determined from neutron diffraction measurements at 15 K: unit-cell constants, a = 9.145 (1) {\AA}, b = 15.557 (3) {\AA}, c = 14.040 (3) {\AA}, β = 106.60 (2)°, monoclinic, space group P21/n, Z = 4, V = 1914.2 (6) {\AA}3, R(F2) = 0.110 for 4859 reflections with F0 2 ≥ 3σ(F0 2) and (sin θ/λ)max = 1.054 {\AA}-1. The Re-H distance (1.827 (4) {\AA}) is longer than the Mn-H distance (1.719 (5) {\AA}). Spectroscopic and crystallographic data indicate that a small amount (∼9{\%}) of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 has cocrystallized with the major component. Further evidence for the identity of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 comes from an independent synthesis by a known route. A mechanism is proposed that accounts for the formation of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 from the reaction of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 with HRe(CO)5. The equilibrium constant for the metal-metal exchange equilibrium, (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 + HRe(CO)5 = (CO)5Re(μ-H)Mn(CO)4Re(CO)5 + HMn(CO)5, has been determined; Keq = 1.00 ± 0.05 at 22 °C in C6D6.",
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T1 - Low-temperature neutron diffraction study of HMn2Re(CO)14 and studies of a metal metal exchange equilibrium that converts HMn2Re(CO)14 into HMnRe2(CO)14

AU - Bullock, R Morris

AU - Brammer, Lee

AU - Schultz, Arthur J.

AU - Albinati, Alberto

AU - Koetzle, Thomas F.

PY - 1992

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N2 - The crystal and molecular structure of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5, prepared from reaction of Mn2-(CO)9(η1-tolualdehyde) with HRe(CO)5, has been determined from neutron diffraction measurements at 15 K: unit-cell constants, a = 9.145 (1) Å, b = 15.557 (3) Å, c = 14.040 (3) Å, β = 106.60 (2)°, monoclinic, space group P21/n, Z = 4, V = 1914.2 (6) Å3, R(F2) = 0.110 for 4859 reflections with F0 2 ≥ 3σ(F0 2) and (sin θ/λ)max = 1.054 Å-1. The Re-H distance (1.827 (4) Å) is longer than the Mn-H distance (1.719 (5) Å). Spectroscopic and crystallographic data indicate that a small amount (∼9%) of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 has cocrystallized with the major component. Further evidence for the identity of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 comes from an independent synthesis by a known route. A mechanism is proposed that accounts for the formation of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 from the reaction of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 with HRe(CO)5. The equilibrium constant for the metal-metal exchange equilibrium, (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 + HRe(CO)5 = (CO)5Re(μ-H)Mn(CO)4Re(CO)5 + HMn(CO)5, has been determined; Keq = 1.00 ± 0.05 at 22 °C in C6D6.

AB - The crystal and molecular structure of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5, prepared from reaction of Mn2-(CO)9(η1-tolualdehyde) with HRe(CO)5, has been determined from neutron diffraction measurements at 15 K: unit-cell constants, a = 9.145 (1) Å, b = 15.557 (3) Å, c = 14.040 (3) Å, β = 106.60 (2)°, monoclinic, space group P21/n, Z = 4, V = 1914.2 (6) Å3, R(F2) = 0.110 for 4859 reflections with F0 2 ≥ 3σ(F0 2) and (sin θ/λ)max = 1.054 Å-1. The Re-H distance (1.827 (4) Å) is longer than the Mn-H distance (1.719 (5) Å). Spectroscopic and crystallographic data indicate that a small amount (∼9%) of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 has cocrystallized with the major component. Further evidence for the identity of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 comes from an independent synthesis by a known route. A mechanism is proposed that accounts for the formation of (CO)5Re(μ-H)Mn(CO)4Re(CO)5 from the reaction of (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 with HRe(CO)5. The equilibrium constant for the metal-metal exchange equilibrium, (CO)5Re(μ-H)Mn(CO)4Mn(CO)5 + HRe(CO)5 = (CO)5Re(μ-H)Mn(CO)4Re(CO)5 + HMn(CO)5, has been determined; Keq = 1.00 ± 0.05 at 22 °C in C6D6.

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