Multiple routes to the formation of a phosphine-bridged trirhodium dihydride cation, [Rh3{μ-(Ph2PCH2)2PPh} 2(H)2(μ-Cl)2(CO)2]+

Alan L. Balch, John Linehan, Marilyn M. Olmstead

Research output: Contribution to journalArticle

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Abstract

Red-orange [Rh3(μ-dpmp)2(H)2(μ-Cl) 2(CO)2][BPh4] (dpmp is bis((diphenylphosphino)methyl)phenylphosphine) is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)2(μ-Cl)Cl][BPh 4] or [Rh3(μ-dpmp)2(μ-CO)(CO)(μ-Cl)Cl][BPh4] with dihydrogen, by the reaction of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous formaldehyde, paraformaldehyde, or acetaldehyde, or by treatment of [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] with dihydrogen. Deep green [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous hydrochloric acid or hydrogen chloride vapor. Spectroscopic data characterizing these complexes are reported. [Rh3(μ-dpmp)2(H)2(CO) 2(μ-Cl)2][BPh4]·3CH 2Cl2 crystallizes in the space group P21/n (No. 14) with a = 14.498 (2) Å, b = 22.077 (3) Å, c = 28.353 (3) Å, β = 99.86 (1)°, and Z = 4 at 130 K, R = 0.049, Rw = 0.054 for 12079 reflections with I > 3σ(I) and 558 parameters. The complex consists of two chloro-bridged A-frame units linked side-by-side through the central rhodium. The hydrides, which were well-behaved on refinement, are primarily localized on the central rhodium; Rh(2)-H distances are 1.48 (7) and 1.55 (7) Å. Structural and 1H NMR spectroscopic evidence suggests a semibridging interaction between these hydrides and the terminal Rh(CO)Cl(P)2 units.

Original languageEnglish
Pages (from-to)3937-3942
Number of pages6
JournalInorganic Chemistry
Volume25
Issue number22
Publication statusPublished - 1986

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phosphine
dihydrides
Carbon Monoxide
phosphines
Cations
routes
rhodium
cations
hydrides
hydrogen chlorides
acetaldehyde
hydrochloric acid
formaldehyde
chlorides
Rhodium
vapors
Hydrochloric Acid
Methylene Chloride
nuclear magnetic resonance
Hydrides

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Multiple routes to the formation of a phosphine-bridged trirhodium dihydride cation, [Rh3{μ-(Ph2PCH2)2PPh} 2(H)2(μ-Cl)2(CO)2]+ . / Balch, Alan L.; Linehan, John; Olmstead, Marilyn M.

In: Inorganic Chemistry, Vol. 25, No. 22, 1986, p. 3937-3942.

Research output: Contribution to journalArticle

@article{55022d090489459fabec5fcf1abc0576,
title = "Multiple routes to the formation of a phosphine-bridged trirhodium dihydride cation, [Rh3{μ-(Ph2PCH2)2PPh} 2(H)2(μ-Cl)2(CO)2]+",
abstract = "Red-orange [Rh3(μ-dpmp)2(H)2(μ-Cl) 2(CO)2][BPh4] (dpmp is bis((diphenylphosphino)methyl)phenylphosphine) is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)2(μ-Cl)Cl][BPh 4] or [Rh3(μ-dpmp)2(μ-CO)(CO)(μ-Cl)Cl][BPh4] with dihydrogen, by the reaction of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous formaldehyde, paraformaldehyde, or acetaldehyde, or by treatment of [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] with dihydrogen. Deep green [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous hydrochloric acid or hydrogen chloride vapor. Spectroscopic data characterizing these complexes are reported. [Rh3(μ-dpmp)2(H)2(CO) 2(μ-Cl)2][BPh4]·3CH 2Cl2 crystallizes in the space group P21/n (No. 14) with a = 14.498 (2) {\AA}, b = 22.077 (3) {\AA}, c = 28.353 (3) {\AA}, β = 99.86 (1)°, and Z = 4 at 130 K, R = 0.049, Rw = 0.054 for 12079 reflections with I > 3σ(I) and 558 parameters. The complex consists of two chloro-bridged A-frame units linked side-by-side through the central rhodium. The hydrides, which were well-behaved on refinement, are primarily localized on the central rhodium; Rh(2)-H distances are 1.48 (7) and 1.55 (7) {\AA}. Structural and 1H NMR spectroscopic evidence suggests a semibridging interaction between these hydrides and the terminal Rh(CO)Cl(P)2 units.",
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T1 - Multiple routes to the formation of a phosphine-bridged trirhodium dihydride cation, [Rh3{μ-(Ph2PCH2)2PPh} 2(H)2(μ-Cl)2(CO)2]+

AU - Balch, Alan L.

AU - Linehan, John

AU - Olmstead, Marilyn M.

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N2 - Red-orange [Rh3(μ-dpmp)2(H)2(μ-Cl) 2(CO)2][BPh4] (dpmp is bis((diphenylphosphino)methyl)phenylphosphine) is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)2(μ-Cl)Cl][BPh 4] or [Rh3(μ-dpmp)2(μ-CO)(CO)(μ-Cl)Cl][BPh4] with dihydrogen, by the reaction of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous formaldehyde, paraformaldehyde, or acetaldehyde, or by treatment of [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] with dihydrogen. Deep green [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous hydrochloric acid or hydrogen chloride vapor. Spectroscopic data characterizing these complexes are reported. [Rh3(μ-dpmp)2(H)2(CO) 2(μ-Cl)2][BPh4]·3CH 2Cl2 crystallizes in the space group P21/n (No. 14) with a = 14.498 (2) Å, b = 22.077 (3) Å, c = 28.353 (3) Å, β = 99.86 (1)°, and Z = 4 at 130 K, R = 0.049, Rw = 0.054 for 12079 reflections with I > 3σ(I) and 558 parameters. The complex consists of two chloro-bridged A-frame units linked side-by-side through the central rhodium. The hydrides, which were well-behaved on refinement, are primarily localized on the central rhodium; Rh(2)-H distances are 1.48 (7) and 1.55 (7) Å. Structural and 1H NMR spectroscopic evidence suggests a semibridging interaction between these hydrides and the terminal Rh(CO)Cl(P)2 units.

AB - Red-orange [Rh3(μ-dpmp)2(H)2(μ-Cl) 2(CO)2][BPh4] (dpmp is bis((diphenylphosphino)methyl)phenylphosphine) is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)2(μ-Cl)Cl][BPh 4] or [Rh3(μ-dpmp)2(μ-CO)(CO)(μ-Cl)Cl][BPh4] with dihydrogen, by the reaction of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous formaldehyde, paraformaldehyde, or acetaldehyde, or by treatment of [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] with dihydrogen. Deep green [Rh3(μ-dpmp)2(μ-CO)2Cl 4][BPh4] is formed by treatment of dichloromethane solutions of [Rh3(μ-dpmp)2(CO)3(μ-Cl)Cl][BPh 4] with aqueous hydrochloric acid or hydrogen chloride vapor. Spectroscopic data characterizing these complexes are reported. [Rh3(μ-dpmp)2(H)2(CO) 2(μ-Cl)2][BPh4]·3CH 2Cl2 crystallizes in the space group P21/n (No. 14) with a = 14.498 (2) Å, b = 22.077 (3) Å, c = 28.353 (3) Å, β = 99.86 (1)°, and Z = 4 at 130 K, R = 0.049, Rw = 0.054 for 12079 reflections with I > 3σ(I) and 558 parameters. The complex consists of two chloro-bridged A-frame units linked side-by-side through the central rhodium. The hydrides, which were well-behaved on refinement, are primarily localized on the central rhodium; Rh(2)-H distances are 1.48 (7) and 1.55 (7) Å. Structural and 1H NMR spectroscopic evidence suggests a semibridging interaction between these hydrides and the terminal Rh(CO)Cl(P)2 units.

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