CO Substitution in HOs 3(CO) 10(μ-SC 6H 4Me-4) by the Diphosphine 4,5-Bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd): Structural and DFT Evaluation of the Isomeric Clusters HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4)

Li Yang; Vladimir N. Nesterov; Xiaoping Wang; Michael G. Richmond

doi:10.1007/s10876-012-0459-x

CO Substitution in HOs ₃(CO) ₁₀(μ-SC ₆H ₄Me-4) by the Diphosphine 4,5-Bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd): Structural and DFT Evaluation of the Isomeric Clusters HOs ₃(CO) ₈(bpcd)(μ-SC ₆H ₄Me-4)

Li Yang, Vladimir N. Nesterov, Xiaoping Wang, Michael G. Richmond

Single Crystal Diffraction

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

12 Scopus citations

Abstract

The reaction of the cluster HOs ₃(CO) ₁₀(μ-SC ₆H ₄Me-4) (1) with the diphosphine 4,5-bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd) has been investigated. 1 reacts with bpcd at room temperature in the presence of Me ₃NO to give the isomeric clusters 1,2-HOs ₃(CO) ₈(bpcd)(μ-SC ₆H ₄Me-4) (2a) and 1,1-HOs ₃(CO) ₈(bpcd)(μ-SC ₆H ₄Me-4) (2b). Clusters 2a and 2b have been isolated, and the molecular structure of each compound has been established by X-ray crystallography. The X-ray structure of 2a confirms the coordination of one of the non-hydride-bridged Os-Os vectors by the bpcd ligand, while the structure of 2b exhibits a chelating bpcd ligand that is bound to one of the osmium centers ligated by the thiolate and hydrido ligands. 2a and 2b are stable in refluxing toluene and show no evidence for bridge-to-chelate isomerization of the ancillary bpcd ligand. DFT calculations on 2a and 2b indicate that the former cluster is the thermodynamically more stable isomer. Near-UV irradiation of 2b leads to CO loss and ortho metalation of the thiolate moiety, yielding the dihydride cluster H ₂Os ₃(CO) ₇(bpcd)(μ,σ-SC ₆H ₃Me-4) (3). The conversion of 2b to 3 and free CO is computed to be endothermic by 14. 1 kcal/mol and the reaction is driven by the entropic release of CO. The photochemically promoted ortho-metalation reaction is isomer dependent since cluster 2a is inert under identical conditions.

Original language	English
Pages (from-to)	685-702
Number of pages	18
Journal	Journal of Cluster Science
Volume	23
Issue number	3
DOIs	https://doi.org/10.1007/s10876-012-0459-x
State	Published - Sep 2012

Funding

Acknowledgments 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. MGR thanks Dr. David A. Hrovat for helpful discussions and 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.

Keywords

DFT
Diphosphine
Ligand substitution
Ortho metalation
Osmium clusters

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@article{aed284e6d1ae4304a9fbabfce3b9b8fa,

title = "CO Substitution in HOs 3(CO) 10(μ-SC 6H 4Me-4) by the Diphosphine 4,5-Bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd): Structural and DFT Evaluation of the Isomeric Clusters HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4)",

abstract = "The reaction of the cluster HOs 3(CO) 10(μ-SC 6H 4Me-4) (1) with the diphosphine 4,5-bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd) has been investigated. 1 reacts with bpcd at room temperature in the presence of Me 3NO to give the isomeric clusters 1,2-HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4) (2a) and 1,1-HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4) (2b). Clusters 2a and 2b have been isolated, and the molecular structure of each compound has been established by X-ray crystallography. The X-ray structure of 2a confirms the coordination of one of the non-hydride-bridged Os-Os vectors by the bpcd ligand, while the structure of 2b exhibits a chelating bpcd ligand that is bound to one of the osmium centers ligated by the thiolate and hydrido ligands. 2a and 2b are stable in refluxing toluene and show no evidence for bridge-to-chelate isomerization of the ancillary bpcd ligand. DFT calculations on 2a and 2b indicate that the former cluster is the thermodynamically more stable isomer. Near-UV irradiation of 2b leads to CO loss and ortho metalation of the thiolate moiety, yielding the dihydride cluster H 2Os 3(CO) 7(bpcd)(μ,σ-SC 6H 3Me-4) (3). The conversion of 2b to 3 and free CO is computed to be endothermic by 14. 1 kcal/mol and the reaction is driven by the entropic release of CO. The photochemically promoted ortho-metalation reaction is isomer dependent since cluster 2a is inert under identical conditions.",

keywords = "DFT, Diphosphine, Ligand substitution, Ortho metalation, Osmium clusters",

author = "Li Yang and Nesterov, {Vladimir N.} and Xiaoping Wang and Richmond, {Michael G.}",

year = "2012",

month = sep,

doi = "10.1007/s10876-012-0459-x",

language = "English",

volume = "23",

pages = "685--702",

journal = "Journal of Cluster Science",

issn = "1040-7278",

publisher = "Springer",

number = "3",

}

Yang, L, Nesterov, VN, Wang, X & Richmond, MG 2012, 'CO Substitution in HOs ₃(CO) ₁₀(μ-SC ₆H ₄Me-4) by the Diphosphine 4,5-Bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd): Structural and DFT Evaluation of the Isomeric Clusters HOs ₃(CO) ₈(bpcd)(μ-SC ₆H ₄Me-4)', Journal of Cluster Science, vol. 23, no. 3, pp. 685-702. https://doi.org/10.1007/s10876-012-0459-x

CO Substitution in HOs ₃(CO) ₁₀(μ-SC ₆H ₄Me-4) by the Diphosphine 4,5-Bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd): Structural and DFT Evaluation of the Isomeric Clusters HOs ₃(CO) ₈(bpcd)(μ-SC ₆H ₄Me-4). / Yang, Li; Nesterov, Vladimir N.; Wang, Xiaoping et al.
In: Journal of Cluster Science, Vol. 23, No. 3, 09.2012, p. 685-702.

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

TY - JOUR

T1 - CO Substitution in HOs 3(CO) 10(μ-SC 6H 4Me-4) by the Diphosphine 4,5-Bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd)

T2 - Structural and DFT Evaluation of the Isomeric Clusters HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4)

AU - Yang, Li

AU - Nesterov, Vladimir N.

AU - Wang, Xiaoping

AU - Richmond, Michael G.

PY - 2012/9

Y1 - 2012/9

N2 - The reaction of the cluster HOs 3(CO) 10(μ-SC 6H 4Me-4) (1) with the diphosphine 4,5-bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd) has been investigated. 1 reacts with bpcd at room temperature in the presence of Me 3NO to give the isomeric clusters 1,2-HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4) (2a) and 1,1-HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4) (2b). Clusters 2a and 2b have been isolated, and the molecular structure of each compound has been established by X-ray crystallography. The X-ray structure of 2a confirms the coordination of one of the non-hydride-bridged Os-Os vectors by the bpcd ligand, while the structure of 2b exhibits a chelating bpcd ligand that is bound to one of the osmium centers ligated by the thiolate and hydrido ligands. 2a and 2b are stable in refluxing toluene and show no evidence for bridge-to-chelate isomerization of the ancillary bpcd ligand. DFT calculations on 2a and 2b indicate that the former cluster is the thermodynamically more stable isomer. Near-UV irradiation of 2b leads to CO loss and ortho metalation of the thiolate moiety, yielding the dihydride cluster H 2Os 3(CO) 7(bpcd)(μ,σ-SC 6H 3Me-4) (3). The conversion of 2b to 3 and free CO is computed to be endothermic by 14. 1 kcal/mol and the reaction is driven by the entropic release of CO. The photochemically promoted ortho-metalation reaction is isomer dependent since cluster 2a is inert under identical conditions.

AB - The reaction of the cluster HOs 3(CO) 10(μ-SC 6H 4Me-4) (1) with the diphosphine 4,5-bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd) has been investigated. 1 reacts with bpcd at room temperature in the presence of Me 3NO to give the isomeric clusters 1,2-HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4) (2a) and 1,1-HOs 3(CO) 8(bpcd)(μ-SC 6H 4Me-4) (2b). Clusters 2a and 2b have been isolated, and the molecular structure of each compound has been established by X-ray crystallography. The X-ray structure of 2a confirms the coordination of one of the non-hydride-bridged Os-Os vectors by the bpcd ligand, while the structure of 2b exhibits a chelating bpcd ligand that is bound to one of the osmium centers ligated by the thiolate and hydrido ligands. 2a and 2b are stable in refluxing toluene and show no evidence for bridge-to-chelate isomerization of the ancillary bpcd ligand. DFT calculations on 2a and 2b indicate that the former cluster is the thermodynamically more stable isomer. Near-UV irradiation of 2b leads to CO loss and ortho metalation of the thiolate moiety, yielding the dihydride cluster H 2Os 3(CO) 7(bpcd)(μ,σ-SC 6H 3Me-4) (3). The conversion of 2b to 3 and free CO is computed to be endothermic by 14. 1 kcal/mol and the reaction is driven by the entropic release of CO. The photochemically promoted ortho-metalation reaction is isomer dependent since cluster 2a is inert under identical conditions.

KW - DFT

KW - Diphosphine

KW - Ligand substitution

KW - Ortho metalation

KW - Osmium clusters

UR - http://www.scopus.com/inward/record.url?scp=84865426901&partnerID=8YFLogxK

U2 - 10.1007/s10876-012-0459-x

DO - 10.1007/s10876-012-0459-x

M3 - Article

AN - SCOPUS:84865426901

SN - 1040-7278

VL - 23

SP - 685

EP - 702

JO - Journal of Cluster Science

JF - Journal of Cluster Science

IS - 3

ER -