Phosphinoborane-induced fragmentation of the unsaturated hydride H 2Re 2(CO) 8: X-ray structure of HRe(CO) 4(κ B,P-Ph 2PCH 2CH 2BR 2) (where BR 2 = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane

Shih Huang Huang; Xiaoping Wang; Michael G. Richmond

doi:10.1016/j.jorganchem.2011.11.020

Phosphinoborane-induced fragmentation of the unsaturated hydride H ₂Re ₂(CO) ₈: X-ray structure of HRe(CO) ₄(κ ^B,P-Ph ₂PCH ₂CH ₂BR ₂) (where BR ₂ = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane

Shih Huang Huang, Xiaoping Wang, Michael G. Richmond

Single Crystal Diffraction

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Abstract

The reactivity of the unsaturated dimer H ₂Re ₂(CO) ₈ (1) with the ambiphilic phosphinoborane Ph ₂PCH ₂CH ₂BR ₂ (2; where BR ₂ = 9-borabicyclo[3.3.1]nonanyl) has been explored. Coordination of the ambiphilic ligand to 1 is rapid at room temperature, leading to the fragmentation of 1 and formation of HRe(CO) ₄(κ ^B,P-Ph ₂PCH ₂CH ₂BR ₂) (3) in high yield. 3 has been characterized in solution by IR and NMR spectroscopy, and the molecular structure established by X-ray diffraction analysis. The solid-state structure confirms the presence of a chelated phosphinoborane ligand through coordination of the phosphine to the rhenium center and the formation of a three-center, two-electron (3c,2e) Re-H-B interaction. The nature of the Re-H-B interaction in 3 has been investigated by DFT, and the energetics for borane dissociation and hydride abstraction by the coordinated Lewis acid in 3 have also been computationally evaluated. The coordination of an oxygen in one of the ancillary CO groups by the pendant borane in HRe(CO) ₄(κ ^P- Ph ₂PCH ₂CH ₂BR ₂) is thermodynamically unfavorable relative to the formation of the 3c,2e Re-H-B bond.

Original language	English
Pages (from-to)	103-109
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	700
DOIs	https://doi.org/10.1016/j.jorganchem.2011.11.020
State	Published - Mar 1 2012

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. MGR acknowledges helpful DFT discussions with Dr. David A. Hrovat (UNT).

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

Ambiphilic ligand
Crystallography
DFT
Phosphinoborane
Rhenium

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Huang, S. H., Wang, X., & Richmond, M. G. (2012). Phosphinoborane-induced fragmentation of the unsaturated hydride H ₂Re ₂(CO) ₈: X-ray structure of HRe(CO) ₄(κ ^B,P-Ph ₂PCH ₂CH ₂BR ₂) (where BR ₂ = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane. Journal of Organometallic Chemistry, 700, 103-109. https://doi.org/10.1016/j.jorganchem.2011.11.020

Huang, Shih Huang ; Wang, Xiaoping ; Richmond, Michael G. / Phosphinoborane-induced fragmentation of the unsaturated hydride H ₂Re ₂(CO) ₈ : X-ray structure of HRe(CO) ₄(κ ^B,P-Ph ₂PCH ₂CH ₂BR ₂) (where BR ₂ = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane. In: Journal of Organometallic Chemistry. 2012 ; Vol. 700. pp. 103-109.

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title = "Phosphinoborane-induced fragmentation of the unsaturated hydride H 2Re 2(CO) 8: X-ray structure of HRe(CO) 4(κ B,P-Ph 2PCH 2CH 2BR 2) (where BR 2 = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane",

abstract = "The reactivity of the unsaturated dimer H 2Re 2(CO) 8 (1) with the ambiphilic phosphinoborane Ph 2PCH 2CH 2BR 2 (2; where BR 2 = 9-borabicyclo[3.3.1]nonanyl) has been explored. Coordination of the ambiphilic ligand to 1 is rapid at room temperature, leading to the fragmentation of 1 and formation of HRe(CO) 4(κ B,P-Ph 2PCH 2CH 2BR 2) (3) in high yield. 3 has been characterized in solution by IR and NMR spectroscopy, and the molecular structure established by X-ray diffraction analysis. The solid-state structure confirms the presence of a chelated phosphinoborane ligand through coordination of the phosphine to the rhenium center and the formation of a three-center, two-electron (3c,2e) Re-H-B interaction. The nature of the Re-H-B interaction in 3 has been investigated by DFT, and the energetics for borane dissociation and hydride abstraction by the coordinated Lewis acid in 3 have also been computationally evaluated. The coordination of an oxygen in one of the ancillary CO groups by the pendant borane in HRe(CO) 4(κ P- Ph 2PCH 2CH 2BR 2) is thermodynamically unfavorable relative to the formation of the 3c,2e Re-H-B bond.",

keywords = "Ambiphilic ligand, Crystallography, DFT, Phosphinoborane, Rhenium",

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Huang, SH, Wang, X & Richmond, MG 2012, 'Phosphinoborane-induced fragmentation of the unsaturated hydride H ₂Re ₂(CO) ₈: X-ray structure of HRe(CO) ₄(κ ^B,P-Ph ₂PCH ₂CH ₂BR ₂) (where BR ₂ = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane', Journal of Organometallic Chemistry, vol. 700, pp. 103-109. https://doi.org/10.1016/j.jorganchem.2011.11.020

Phosphinoborane-induced fragmentation of the unsaturated hydride H ₂Re ₂(CO) ₈: X-ray structure of HRe(CO) ₄(κ ^B,P-Ph ₂PCH ₂CH ₂BR ₂) (where BR ₂ = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane. / Huang, Shih Huang; Wang, Xiaoping; Richmond, Michael G.
In: Journal of Organometallic Chemistry, Vol. 700, 01.03.2012, p. 103-109.

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

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T1 - Phosphinoborane-induced fragmentation of the unsaturated hydride H 2Re 2(CO) 8

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AU - Huang, Shih Huang

AU - Wang, Xiaoping

AU - Richmond, Michael G.

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N2 - The reactivity of the unsaturated dimer H 2Re 2(CO) 8 (1) with the ambiphilic phosphinoborane Ph 2PCH 2CH 2BR 2 (2; where BR 2 = 9-borabicyclo[3.3.1]nonanyl) has been explored. Coordination of the ambiphilic ligand to 1 is rapid at room temperature, leading to the fragmentation of 1 and formation of HRe(CO) 4(κ B,P-Ph 2PCH 2CH 2BR 2) (3) in high yield. 3 has been characterized in solution by IR and NMR spectroscopy, and the molecular structure established by X-ray diffraction analysis. The solid-state structure confirms the presence of a chelated phosphinoborane ligand through coordination of the phosphine to the rhenium center and the formation of a three-center, two-electron (3c,2e) Re-H-B interaction. The nature of the Re-H-B interaction in 3 has been investigated by DFT, and the energetics for borane dissociation and hydride abstraction by the coordinated Lewis acid in 3 have also been computationally evaluated. The coordination of an oxygen in one of the ancillary CO groups by the pendant borane in HRe(CO) 4(κ P- Ph 2PCH 2CH 2BR 2) is thermodynamically unfavorable relative to the formation of the 3c,2e Re-H-B bond.

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KW - Ambiphilic ligand

KW - Crystallography

KW - DFT

KW - Phosphinoborane

KW - Rhenium

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Huang SH, Wang X, Richmond MG. Phosphinoborane-induced fragmentation of the unsaturated hydride H ₂Re ₂(CO) ₈: X-ray structure of HRe(CO) ₄(κ ^B,P-Ph ₂PCH ₂CH ₂BR ₂) (where BR ₂ = 9-borabicyclo[3.3.1]nonanyl) and DFT Evaluation of hydride versus CO coordination by the ancillary borane. Journal of Organometallic Chemistry. 2012 Mar 1;700:103-109. doi: 10.1016/j.jorganchem.2011.11.020