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.
- Authors:
-
- Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Sciences Directorate
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1261414
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Cluster Science
- Additional Journal Information:
- Journal Volume: 26; Journal Issue: 1; Journal ID: ISSN 1040-7278
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Osmium clusters; Ligand substitution; Diphosphine ligand activation; X-ray crystallography; DFT
Citation Formats
Yang, Li, Nesterov, Vladimir N., Wang, Xiaoping, and Richmond, Michael G. 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. United States: N. p., 2014.
Web. doi:10.1007/s10876-014-0756-7.
Yang, Li, Nesterov, Vladimir N., Wang, Xiaoping, & Richmond, Michael G. 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. United States. https://doi.org/10.1007/s10876-014-0756-7
Yang, Li, Nesterov, Vladimir N., Wang, Xiaoping, and Richmond, Michael G. Wed .
"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". United States. https://doi.org/10.1007/s10876-014-0756-7. https://www.osti.gov/servlets/purl/1261414.
@article{osti_1261414,
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},
author = {Yang, Li and Nesterov, Vladimir N. and Wang, Xiaoping and Richmond, Michael G.},
abstractNote = {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.},
doi = {10.1007/s10876-014-0756-7},
journal = {Journal of Cluster Science},
number = 1,
volume = 26,
place = {United States},
year = {Wed Jul 23 00:00:00 EDT 2014},
month = {Wed Jul 23 00:00:00 EDT 2014}
}
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Works referenced in this record:
Asymmetric hydrogenation in the presence of bicyclic chiral phosphines
journal, June 1981
- Kreuzfeld, H. -J.; Döbler, Chr
- Reaction Kinetics and Catalysis Letters, Vol. 16, Issue 2-3
Asymmetrische Katalysen
journal, August 1991
- Brunner, Henri; Prester, Franz
- Journal of Organometallic Chemistry, Vol. 414, Issue 3
Effect of the structure and concentration of diphosphine ligands on the rate of hydrocarbomethoxylation of cyclohexene catalyzed by palladium acetate/diphosphine/TsOH system
journal, November 2011
- Nifant’ev, I. E.; Batashev, S. A.; Toloraya, S. A.
- Journal of Molecular Catalysis A: Chemical, Vol. 350, Issue 1-2
Steric and electronic factors in the promoting activity of diphosphine ligands in cyclohexene hydrocarbomethoxylation catalyzed by palladium acetate
journal, July 2012
- Nifant’ev, I. E.; Batashev, S. A.; Toloraya, S. A.
- Kinetics and Catalysis, Vol. 53, Issue 4
Ligand Substitution Chemistry of the Diphosphine Ligand endo,endo-2,3-Bis(diphenylphosphinomethyl)-5-norbornene (dpmn): Syntheses and X-ray Diffraction Structures of PtCl2(dmn) and PtMe2(dpmn)
journal, April 2009
- Watson, William H.; Huang, Shih-Huang; Yang, Li
- Journal of Chemical Crystallography, Vol. 39, Issue 10
Reversible Isomerization of a Diphosphine Ligand about a Triosmium Cluster: Synthesis, Kinetics, and X-ray Structures for the Bridging and Chelating Isomers of Os3(CO)10[(Z)-Ph2PCHCHPPh2]
journal, September 2005
- Watson, William H.; Wu, Guanmin; Richmond, Michael G.
- Organometallics, Vol. 24, Issue 22
Diphosphine Isomerization and C−H and P−C Bond Cleavage Reactivity in the Triosmium Cluster Os3(CO)10(bpcd): Kinetic and Isotope Data for Reversible Ortho Metalation and X-ray Structures of the Bridging and Chelating Isomers of Os3(CO)10(bpcd) and the Benzyne-Substituted Cluster HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhCC(PPh2)C(O)CH2C(O)]
journal, January 2006
- Watson, William H.; Wu, Guanmin; Richmond, Michael G.
- Organometallics, Vol. 25, Issue 4
Experimental and Computational Studies of the Isomerization Reactions of Bidentate Phosphine Ligands in Triosmium Clusters: Kinetics of the Rearrangements from Bridged to Chelated Isomers and X-ray Structures of the Clusters Os3(CO)10(dppbz), 1,1-Os3(CO)10(dppbzF4), HOs3(CO)9[μ-1,2-PhP(C6H4-η1)C6H4PPh2], and HOs3(CO)9[μ-1,2-PhP(C6H4-η1)C6F4PPh2]
journal, February 2011
- Zhang, Xue; Kandala, Srikanth; Yang, Li
- Organometallics, Vol. 30, Issue 5
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-C6H4)(Ph2P)quinoxaline]
journal, April 2011
- Hunt, Sean W.; Yang, Li; Wang, Xiaoping
- Journal of Organometallic Chemistry, Vol. 696, Issue 7
Some Useful Derivatives of Dodecacarbonyltriosmium
book, January 2007
- Nicholls, J. N.; Vargas, M. D.; Deeming, A. J.
- Inorganic Syntheses, Vol. 26
Zur Darstellung der Enantiomeren des trans-2,3-Bis-(diphenylphosphinomethyl)-norbornen-(5)
journal, January 1981
- Döbler, Chr.; Kreuzfeld, H. -J.
- Journal für Praktische Chemie, Vol. 323, Issue 4
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Single-crystal structure validation with the program PLATON
journal, January 2003
- Spek, A. L.
- Journal of Applied Crystallography, Vol. 36, Issue 1, p. 7-13
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
journal, September 1988
- Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank
- Chemical Reviews, Vol. 88, Issue 6
Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane
journal, January 1968
- Wiberg, K. B.
- Tetrahedron, Vol. 24, Issue 3
Remarkable Differences in Catalyst Activity and Selectivity for the Production of Methyl Propanoate versus CO−Ethylene Copolymer by a Series of Palladium Complexes of Related C4-Bridged Diphosphines
journal, October 2000
- Knight, Julian G.; Doherty, Simon; Harriman, Anthony
- Organometallics, Vol. 19, Issue 24
Triphenylphosphine-substituted selenido and sulfido clusters of osmium derived from Ph3PSe or Ph3PS
journal, November 2005
- Akter, Hamida; Deeming, Antony J.; Golzar Hossain, G. M.
- Journal of Organometallic Chemistry, Vol. 690, Issue 21-22
Chelate and Bridge Diphosphine Isomerization: Triosmium and Triruthenium Clusters Containing 1,1‘-Bis(diphenylphosphino)ferrocene (dppf)
journal, October 2007
- Begum, Noorjahan; Das, Uttam K.; Hassan, Manzur
- Organometallics, Vol. 26, Issue 25
Triosmium clusters derived from the reactions of thioureas with dodecacarbonyltriosmium: Crystal structures of [Os3(CO)11{η 1-SC(NMe2)2}], [Os3(CO)9(μ-OH)(μ-OMeOCO){η 1-SC(NMe2)2}] and [(μ-H)Os3(CO)9{μ 3-NHC(S)NH2}]
journal, March 1996
- Azam, Kazi A.; Dilshad, Rahima; Kabir, Shariff E.
- Journal of Cluster Science, Vol. 7, Issue 1
Reaction of [N(PPh3)2][Os3(μ-H)(CO)11] with [Cu(PPh3)2BH4]. Crystal and molecular structures of [Os3(μ-H)(μ-OH)(CO)10] and two [Os3(μ-H)(μ-OH)(CO)8(PPh3)2] isomeric clusters
journal, September 1995
- Ho, Winnie Ging-Yee; Wong, Wing-Tak
- Polyhedron, Vol. 14, Issue 20-21
Complexes containing bridging tin- and germanium-substituted metallocarboxylate ligands from the reactions of Ph3SnOH and Ph3GeOH with Os3(CO)12 in the presence of base
journal, August 2011
- Adams, Richard D.; Chen, Mingwei; Trufan, Eszter
- Journal of Organometallic Chemistry, Vol. 696, Issue 17
The molecular structures of H2Os3(CO)10, H(SC2H5)Os3(CO)10 and (OCH3)2Os3(CO)10
journal, November 1977
- Allen, Valerie F.; Mason, Ronald; Hitchcock, Peter B.
- Journal of Organometallic Chemistry, Vol. 140, Issue 3
Reduced Overlap Population Analysis for Triosmium Clusters
journal, July 2007
- Morrison, Elizabeth C.; Leong, Weng Kee; Tan, Jialin
- Journal of Cluster Science, Vol. 18, Issue 3
Bimetallic osmium-tin complexes: Stannylene and hydrostannylene clusters upon addition of Ph3SnH to unsaturated triosmium clusters [(μ-H)2Os3(CO)8(μ-diphosphine)] (diphosphine = dppm, dppf)
journal, January 2014
- Sarker, Jagodish C.; Uddin, Kh. Mahid; Rahman, Md. Saifur
- Inorganica Chimica Acta, Vol. 409
DFT Investigation of the Mechanism of Phosphine-Thioether Isomerization in the Triosmium Cluster Os3(CO)10(Ph2PCH2CH2SMe): Migratory Preference for the Formation of an Edge-Bridged Thioether versus a Phosphine Moiety
journal, September 2012
- Hrovat, David A.; Nordlander, Ebbe; Richmond, Michael G.
- Organometallics, Vol. 31, Issue 18
2-[(Diphenylphosphino)methyl]-6-methylpyridine (PN) coordination chemistry at triosmium clusters: Regiospecific ligand activation and DFT evaluation of the isomeric Os3(CO)10(PN) clusters
journal, November 2013
- Lin, Chen-Hao; Nesterov, Vladimir N.; Richmond, Michael G.
- Journal of Organometallic Chemistry, Vol. 744
CO Substitution in HOs3(CO)10(μ-SC6H4Me-4) by the Diphosphine 4,5-Bis(diphenylphosphino)-4-cyclopentadiene-1,3-dione (bpcd): Structural and DFT Evaluation of the Isomeric Clusters HOs3(CO)8(bpcd)(μ-SC6H4Me-4)
journal, March 2012
- Yang, Li; Nesterov, Vladimir N.; Wang, Xiaoping
- Journal of Cluster Science, Vol. 23, Issue 3