Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10(trans-dpmn) and 1,2-Os3(CO)10(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os3(CO)10(dpmn) and Isomer-Dependent Diphosphine Ligand Activation

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

doi:10.1007/s10876-014-0756-7

Synthesis of the Stereoisomeric Clusters 1,2-Os₃(CO)₁₀(trans-dpmn) and 1,2-Os₃(CO)₁₀(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os₃(CO)₁₀(dpmn) and Isomer-Dependent Diphosphine Ligand Activation

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

Single Crystal Diffraction

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

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Abstract

The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os₃(CO)₁₀(MeCN)₂ (1) to furnish the corresponding ligand-bridged clusters Os₃(CO)₁₀(trans-dpmn) (2) and Os₃(CO)₁₀(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os₃(CO)₈(µ-OH)₂(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373 K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C–H bonds and one P–C(phenyl) bond, to furnish the dihydride cluster H₂Os₃(CO)₈[µ₃-2-PhPC-3-endo-Ph₂PCH₂(C₇H₇)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph₂PCH₂(C₇H₇) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3 → 5 + 2CO + benzene is computed to be exergonic by 12.7 kcal/mol and is entropically favored due to the release of the CO and benzene by-products.

Original language	English
Pages (from-to)	93-109
Number of pages	17
Journal	Journal of Cluster Science
Volume	26
Issue number	1
DOIs	https://doi.org/10.1007/s10876-014-0756-7
State	Published - Jan 2015

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 (CHE-0741936) of the computational facilities at UNT is also acknowledged. MGR thanks 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 activation
Ligand substitution
Osmium clusters
X-ray crystallography

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Yang, L., Nesterov, V. N., Wang, X., & Richmond, M. G. (2015). Synthesis of the Stereoisomeric Clusters 1,2-Os₃(CO)₁₀(trans-dpmn) and 1,2-Os₃(CO)₁₀(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os₃(CO)₁₀(dpmn) and Isomer-Dependent Diphosphine Ligand Activation. Journal of Cluster Science, 26(1), 93-109. https://doi.org/10.1007/s10876-014-0756-7

Yang, Li ; Nesterov, Vladimir N. ; Wang, Xiaoping et al. / Synthesis of the Stereoisomeric Clusters 1,2-Os₃(CO)₁₀(trans-dpmn) and 1,2-Os₃(CO)₁₀(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene] : DFT Evaluation of the Isomeric Clusters 1,2-Os₃(CO)₁₀(dpmn) and Isomer-Dependent Diphosphine Ligand Activation. In: Journal of Cluster Science. 2015 ; Vol. 26, No. 1. pp. 93-109.

@article{55f37a0a3f4a4b33997cad8902c2c5e0,

title = "Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10(trans-dpmn) and 1,2-Os3(CO)10(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os3(CO)10(dpmn) and Isomer-Dependent Diphosphine Ligand Activation",

abstract = "The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os3(CO)10(MeCN)2 (1) to furnish the corresponding ligand-bridged clusters Os3(CO)10(trans-dpmn) (2) and Os3(CO)10(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os3(CO)8(µ-OH)2(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373 K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C–H bonds and one P–C(phenyl) bond, to furnish the dihydride cluster H2Os3(CO)8[µ3-2-PhPC-3-endo-Ph2PCH2(C7H7)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph2PCH2(C7H7) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3 → 5 + 2CO + benzene is computed to be exergonic by 12.7 kcal/mol and is entropically favored due to the release of the CO and benzene by-products.",

keywords = "DFT, Diphosphine ligand activation, Ligand substitution, Osmium clusters, X-ray crystallography",

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

note = "Publisher Copyright: {\textcopyright} 2014, Springer Science+Business Media New York.",

year = "2015",

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doi = "10.1007/s10876-014-0756-7",

language = "English",

volume = "26",

pages = "93--109",

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Yang, L, Nesterov, VN, Wang, X & Richmond, MG 2015, 'Synthesis of the Stereoisomeric Clusters 1,2-Os₃(CO)₁₀(trans-dpmn) and 1,2-Os₃(CO)₁₀(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os₃(CO)₁₀(dpmn) and Isomer-Dependent Diphosphine Ligand Activation', Journal of Cluster Science, vol. 26, no. 1, pp. 93-109. https://doi.org/10.1007/s10876-014-0756-7

Synthesis of the Stereoisomeric Clusters 1,2-Os₃(CO)₁₀(trans-dpmn) and 1,2-Os₃(CO)₁₀(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os₃(CO)₁₀(dpmn) and Isomer-Dependent Diphosphine Ligand Activation. / Yang, Li; Nesterov, Vladimir N.; Wang, Xiaoping et al.
In: Journal of Cluster Science, Vol. 26, No. 1, 01.2015, p. 93-109.

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

TY - JOUR

T1 - Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10(trans-dpmn) and 1,2-Os3(CO)10(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]

T2 - DFT Evaluation of the Isomeric Clusters 1,2-Os3(CO)10(dpmn) and Isomer-Dependent Diphosphine Ligand Activation

AU - Yang, Li

AU - Nesterov, Vladimir N.

AU - Wang, Xiaoping

AU - Richmond, Michael G.

PY - 2015/1

Y1 - 2015/1

N2 - The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os3(CO)10(MeCN)2 (1) to furnish the corresponding ligand-bridged clusters Os3(CO)10(trans-dpmn) (2) and Os3(CO)10(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os3(CO)8(µ-OH)2(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373 K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C–H bonds and one P–C(phenyl) bond, to furnish the dihydride cluster H2Os3(CO)8[µ3-2-PhPC-3-endo-Ph2PCH2(C7H7)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph2PCH2(C7H7) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3 → 5 + 2CO + benzene is computed to be exergonic by 12.7 kcal/mol and is entropically favored due to the release of the CO and benzene by-products.

AB - The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os3(CO)10(MeCN)2 (1) to furnish the corresponding ligand-bridged clusters Os3(CO)10(trans-dpmn) (2) and Os3(CO)10(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os3(CO)8(µ-OH)2(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373 K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C–H bonds and one P–C(phenyl) bond, to furnish the dihydride cluster H2Os3(CO)8[µ3-2-PhPC-3-endo-Ph2PCH2(C7H7)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph2PCH2(C7H7) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3 → 5 + 2CO + benzene is computed to be exergonic by 12.7 kcal/mol and is entropically favored due to the release of the CO and benzene by-products.

KW - DFT

KW - Diphosphine ligand activation

KW - Ligand substitution

KW - Osmium clusters

KW - X-ray crystallography

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DO - 10.1007/s10876-014-0756-7

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SN - 1040-7278

VL - 26

SP - 93

EP - 109

JO - Journal of Cluster Science

JF - Journal of Cluster Science

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ER -

Yang L, Nesterov VN, Wang X, Richmond MG. Synthesis of the Stereoisomeric Clusters 1,2-Os₃(CO)₁₀(trans-dpmn) and 1,2-Os₃(CO)₁₀(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os₃(CO)₁₀(dpmn) and Isomer-Dependent Diphosphine Ligand Activation. Journal of Cluster Science. 2015 Jan;26(1):93-109. doi: 10.1007/s10876-014-0756-7

Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10(trans-dpmn) and 1,2-Os3(CO)10(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os3(CO)10(dpmn) and Isomer-Dependent Diphosphine Ligand Activation