New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq): Ligand isomerization and crystal structures of dppq, the isomeric clusters Os3(CO)10(dppq), and HOs3(CO)9[μ-2,3-PhP(η1-C 6H4)(Ph2P)quinoxaline]

Sean W. Hunt; Li Yang; Xiaoping Wang; Michael G. Richmond

doi:10.1016/j.jorganchem.2011.01.019

New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq): Ligand isomerization and crystal structures of dppq, the isomeric clusters Os₃(CO)₁₀(dppq), and HOs₃(CO)₉[μ-2,3-PhP(η¹-C ₆H₄)(Ph₂P)quinoxaline]

Sean W. Hunt, Li Yang, Xiaoping Wang, Michael G. Richmond

Single Crystal Diffraction

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

Treatment of the labile cluster 1,2-Os₃(CO)₁₀(MeCN) ₂ (1) with the diphosphine ligand 2,3-bis(diphenylphosphino) quinoxaline (dppq) at room temperature affords 1,2-Os₃(CO) ₁₀(dppq) (2b) as the kinetic product of ligand substitution in 84% yield. 2b isomerizes to the thermodynamically more stable dppq-chelated cluster 1,1-Os₃(CO)₁₀(dppq) (2c) as the sole observable product under CO at temperatures below 358 K. The kinetics for the conversion of 2b → 2c have been investigated by NMR spectroscopy in CDCl₃ over the temperature range 323-353 K, and the reaction was found to exhibit a rate law that is first order in 2b. The calculated activation parameters [ΔH^≠ = 25.4(4) kcal/mol; ΔS^≠ = -3(1) eu] support an intramolecular isomerization scenario, one that involves the migration of phosphine and CO groups about the cluster polyhedron. The disposition of the dppq ligand in the isomeric Os₃(CO) ₁₀(dppq) clusters has been established by X-ray crystallography and ³¹P NMR spectroscopy. Photolysis of 2c at 366 nm leads to CO loss and ortho metalation of one of the aryl groups on the Ph₂P moiety to furnish the hydride cluster HOs₃(CO)₉[μ- PhP(η¹-C₆H₄)(Ph₂P)quinoxaline] (3). The isomerization behavior exhibited by 2b follows that of related diphosphine-substituted Os₃ clusters prepared by us.

Original language	English
Pages (from-to)	1432-1440
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	696
Issue number	7
DOIs	https://doi.org/10.1016/j.jorganchem.2011.01.019
State	Published - Apr 1 2011

Funding

Financial support from the Robert A. Welch Foundation (Grant B-1093-MGR ) is greatly appreciated, and X. Wang acknowledges support by the U.S. Department of Energy, Office of Science , under Contract No. DE-AC05-00OR22725 managed by UT Battelle, LLC. NSF support of the NMR and computational facilities at UNT through grants CHE-0840518 and CHE-0741936 is acknowledged. We also wish to thank Prof. Michael B. Hall (TAMU) for providing us a copy of his JIMP2 program, which was used to prepare the geometry-optimized structures reported here, and Dr. David A. Hrovat (Center for Advanced Scientific Computing and Modeling, UNT) for his assistance and guidance with computational aspects for this work.

Funders	Funder number
Robert A. Welch Foundation	B-1093-MGR
U.S. Department of Energy
Office of Science
University of North Texas	CHE-0741936, CHE-0840518

Keywords

Crystallography
Diphosphine isomerization
Osmium clusters
P-C bond activation
Redox properties

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Hunt, S. W., Yang, L., Wang, X., & Richmond, M. G. (2011). New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq): Ligand isomerization and crystal structures of dppq, the isomeric clusters Os₃(CO)₁₀(dppq), and HOs₃(CO)₉[μ-2,3-PhP(η¹-C ₆H₄)(Ph₂P)quinoxaline]. Journal of Organometallic Chemistry, 696(7), 1432-1440. https://doi.org/10.1016/j.jorganchem.2011.01.019

Hunt, Sean W. ; Yang, Li ; Wang, Xiaoping et al. / New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq) : Ligand isomerization and crystal structures of dppq, the isomeric clusters Os₃(CO)₁₀(dppq), and HOs₃(CO)₉[μ-2,3-PhP(η¹-C ₆H₄)(Ph₂P)quinoxaline]. In: Journal of Organometallic Chemistry. 2011 ; Vol. 696, No. 7. pp. 1432-1440.

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title = "New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq): Ligand isomerization and crystal structures of dppq, the isomeric clusters Os3(CO)10(dppq), and HOs3(CO)9[μ-2,3-PhP(η1-C 6H4)(Ph2P)quinoxaline]",

abstract = "Treatment of the labile cluster 1,2-Os3(CO)10(MeCN) 2 (1) with the diphosphine ligand 2,3-bis(diphenylphosphino) quinoxaline (dppq) at room temperature affords 1,2-Os3(CO) 10(dppq) (2b) as the kinetic product of ligand substitution in 84% yield. 2b isomerizes to the thermodynamically more stable dppq-chelated cluster 1,1-Os3(CO)10(dppq) (2c) as the sole observable product under CO at temperatures below 358 K. The kinetics for the conversion of 2b → 2c have been investigated by NMR spectroscopy in CDCl3 over the temperature range 323-353 K, and the reaction was found to exhibit a rate law that is first order in 2b. The calculated activation parameters [ΔH≠ = 25.4(4) kcal/mol; ΔS≠ = -3(1) eu] support an intramolecular isomerization scenario, one that involves the migration of phosphine and CO groups about the cluster polyhedron. The disposition of the dppq ligand in the isomeric Os3(CO) 10(dppq) clusters has been established by X-ray crystallography and 31P NMR spectroscopy. Photolysis of 2c at 366 nm leads to CO loss and ortho metalation of one of the aryl groups on the Ph2P moiety to furnish the hydride cluster HOs3(CO)9[μ- PhP(η1-C6H4)(Ph2P)quinoxaline] (3). The isomerization behavior exhibited by 2b follows that of related diphosphine-substituted Os3 clusters prepared by us.",

keywords = "Crystallography, Diphosphine isomerization, Osmium clusters, P-C bond activation, Redox properties",

author = "Hunt, {Sean W.} and Li Yang and Xiaoping Wang and Richmond, {Michael G.}",

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Hunt, SW, Yang, L, Wang, X & Richmond, MG 2011, 'New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq): Ligand isomerization and crystal structures of dppq, the isomeric clusters Os₃(CO)₁₀(dppq), and HOs₃(CO)₉[μ-2,3-PhP(η¹-C ₆H₄)(Ph₂P)quinoxaline]', Journal of Organometallic Chemistry, vol. 696, no. 7, pp. 1432-1440. https://doi.org/10.1016/j.jorganchem.2011.01.019

New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq): Ligand isomerization and crystal structures of dppq, the isomeric clusters Os₃(CO)₁₀(dppq), and HOs₃(CO)₉[μ-2,3-PhP(η¹-C ₆H₄)(Ph₂P)quinoxaline]. / Hunt, Sean W.; Yang, Li; Wang, Xiaoping et al.
In: Journal of Organometallic Chemistry, Vol. 696, No. 7, 01.04.2011, p. 1432-1440.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq)

T2 - Ligand isomerization and crystal structures of dppq, the isomeric clusters Os3(CO)10(dppq), and HOs3(CO)9[μ-2,3-PhP(η1-C 6H4)(Ph2P)quinoxaline]

AU - Hunt, Sean W.

AU - Yang, Li

AU - Wang, Xiaoping

AU - Richmond, Michael G.

PY - 2011/4/1

Y1 - 2011/4/1

N2 - Treatment of the labile cluster 1,2-Os3(CO)10(MeCN) 2 (1) with the diphosphine ligand 2,3-bis(diphenylphosphino) quinoxaline (dppq) at room temperature affords 1,2-Os3(CO) 10(dppq) (2b) as the kinetic product of ligand substitution in 84% yield. 2b isomerizes to the thermodynamically more stable dppq-chelated cluster 1,1-Os3(CO)10(dppq) (2c) as the sole observable product under CO at temperatures below 358 K. The kinetics for the conversion of 2b → 2c have been investigated by NMR spectroscopy in CDCl3 over the temperature range 323-353 K, and the reaction was found to exhibit a rate law that is first order in 2b. The calculated activation parameters [ΔH≠ = 25.4(4) kcal/mol; ΔS≠ = -3(1) eu] support an intramolecular isomerization scenario, one that involves the migration of phosphine and CO groups about the cluster polyhedron. The disposition of the dppq ligand in the isomeric Os3(CO) 10(dppq) clusters has been established by X-ray crystallography and 31P NMR spectroscopy. Photolysis of 2c at 366 nm leads to CO loss and ortho metalation of one of the aryl groups on the Ph2P moiety to furnish the hydride cluster HOs3(CO)9[μ- PhP(η1-C6H4)(Ph2P)quinoxaline] (3). The isomerization behavior exhibited by 2b follows that of related diphosphine-substituted Os3 clusters prepared by us.

AB - Treatment of the labile cluster 1,2-Os3(CO)10(MeCN) 2 (1) with the diphosphine ligand 2,3-bis(diphenylphosphino) quinoxaline (dppq) at room temperature affords 1,2-Os3(CO) 10(dppq) (2b) as the kinetic product of ligand substitution in 84% yield. 2b isomerizes to the thermodynamically more stable dppq-chelated cluster 1,1-Os3(CO)10(dppq) (2c) as the sole observable product under CO at temperatures below 358 K. The kinetics for the conversion of 2b → 2c have been investigated by NMR spectroscopy in CDCl3 over the temperature range 323-353 K, and the reaction was found to exhibit a rate law that is first order in 2b. The calculated activation parameters [ΔH≠ = 25.4(4) kcal/mol; ΔS≠ = -3(1) eu] support an intramolecular isomerization scenario, one that involves the migration of phosphine and CO groups about the cluster polyhedron. The disposition of the dppq ligand in the isomeric Os3(CO) 10(dppq) clusters has been established by X-ray crystallography and 31P NMR spectroscopy. Photolysis of 2c at 366 nm leads to CO loss and ortho metalation of one of the aryl groups on the Ph2P moiety to furnish the hydride cluster HOs3(CO)9[μ- PhP(η1-C6H4)(Ph2P)quinoxaline] (3). The isomerization behavior exhibited by 2b follows that of related diphosphine-substituted Os3 clusters prepared by us.

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KW - Diphosphine isomerization

KW - Osmium clusters

KW - P-C bond activation

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Hunt SW, Yang L, Wang X, Richmond MG. New osmium cluster compounds containing the heterocyclic ligand 2,3-bis-(diphenylphosphino)quinoxaline (dppq): Ligand isomerization and crystal structures of dppq, the isomeric clusters Os₃(CO)₁₀(dppq), and HOs₃(CO)₉[μ-2,3-PhP(η¹-C ₆H₄)(Ph₂P)quinoxaline]. Journal of Organometallic Chemistry. 2011 Apr 1;696(7):1432-1440. doi: 10.1016/j.jorganchem.2011.01.019