Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf): Synthesis and X-ray diffraction structures of the isomeric Os3(CO) 10(bmf) clusters and HOs3(CO)8(μ-C 6H4)

Srikanth Kandala; Li Yang; Charles F. Campana; Vladimir Nesterov; Xiaoping Wang; Michael G. Richmond

doi:10.1016/j.poly.2010.07.003

Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os₃(CO)₉(bmf): Synthesis and X-ray diffraction structures of the isomeric Os₃(CO) ₁₀(bmf) clusters and HOs₃(CO)₈(μ-C ₆H₄)

Srikanth Kandala
, Li Yang
, Charles F. Campana
, Vladimir Nesterov
, Xiaoping Wang
, Michael G. Richmond

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

5 Scopus citations

Abstract

The labile cluster 1,2-Os₃(CO)₁₀(MeCN)₂ (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os₃(CO)₁₀(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358-383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os₃(CO)₁₀(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os₃(CO)₁₀(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs ₃(CO)₉(C₂₉H₂₃O₃P ₂) (3a-c). Thermolysis of HOs₃(CO)₉(C ₂₉H₂₃O₃P₂) (3a-c) in refluxing toluene leads to P-C bond cleavage and formation of the benzyne-substituted clusters HOs₃(CO)₈(μ-C₆H₄)(μ- C₂₃H₁₉O₃P₂) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated α to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os₃(CO)₁₀(diphosphine) derivatives prepared by our groups.

Original language	English
Pages (from-to)	2814-2821
Number of pages	8
Journal	Polyhedron
Volume	29
Issue number	14
DOIs	https://doi.org/10.1016/j.poly.2010.07.003
State	Published - Sep 22 2010

Funding

Financial support from the Robert A. Welch Foundation (Grant B-1093-MGR) is greatly appreciated. X. Wang acknowledges the support by the US Department of Energy, Office of Science, under Contract No. DE-AC05-00OR22725 managed by UT Battelle, LLC. Prof. Arnold Rheingold is thanked for his hospitality and the use of his X-ray diffractometer that was used to collect the X-ray data on the isomeric clusters 2a,b during the 2004 ACS-PRF summer school on Crystallography for Organic Chemists.

Keywords

Crystallography
Diphosphine ligand
Ligand substitution
Osmium clusters
P-C bond-activation

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Kandala, S., Yang, L., Campana, C. F., Nesterov, V., Wang, X., & Richmond, M. G. (2010). Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os₃(CO)₉(bmf): Synthesis and X-ray diffraction structures of the isomeric Os₃(CO) ₁₀(bmf) clusters and HOs₃(CO)₈(μ-C ₆H₄). Polyhedron, 29(14), 2814-2821. https://doi.org/10.1016/j.poly.2010.07.003

Kandala, Srikanth ; Yang, Li ; Campana, Charles F. et al. / Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os₃(CO)₉(bmf) : Synthesis and X-ray diffraction structures of the isomeric Os₃(CO) ₁₀(bmf) clusters and HOs₃(CO)₈(μ-C ₆H₄). In: Polyhedron. 2010 ; Vol. 29, No. 14. pp. 2814-2821.

@article{0686b76631214cb6968e22c9caa4feac,

title = "Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf): Synthesis and X-ray diffraction structures of the isomeric Os3(CO) 10(bmf) clusters and HOs3(CO)8(μ-C 6H4)",

abstract = "The labile cluster 1,2-Os3(CO)10(MeCN)2 (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os3(CO)10(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358-383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os3(CO)10(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os3(CO)10(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs 3(CO)9(C29H23O3P 2) (3a-c). Thermolysis of HOs3(CO)9(C 29H23O3P2) (3a-c) in refluxing toluene leads to P-C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)8(μ-C6H4)(μ- C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated α to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os3(CO)10(diphosphine) derivatives prepared by our groups.",

keywords = "Crystallography, Diphosphine ligand, Ligand substitution, Osmium clusters, P-C bond-activation",

author = "Srikanth Kandala and Li Yang and Campana, \{Charles F.\} and Vladimir Nesterov and Xiaoping Wang and Richmond, \{Michael G.\}",

year = "2010",

month = sep,

day = "22",

doi = "10.1016/j.poly.2010.07.003",

language = "English",

volume = "29",

pages = "2814--2821",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier",

number = "14",

}

Kandala, S, Yang, L, Campana, CF, Nesterov, V, Wang, X & Richmond, MG 2010, 'Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os₃(CO)₉(bmf): Synthesis and X-ray diffraction structures of the isomeric Os₃(CO) ₁₀(bmf) clusters and HOs₃(CO)₈(μ-C ₆H₄)', Polyhedron, vol. 29, no. 14, pp. 2814-2821. https://doi.org/10.1016/j.poly.2010.07.003

Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os₃(CO)₉(bmf): Synthesis and X-ray diffraction structures of the isomeric Os₃(CO) ₁₀(bmf) clusters and HOs₃(CO)₈(μ-C ₆H₄). / Kandala, Srikanth; Yang, Li; Campana, Charles F. et al.
In: Polyhedron, Vol. 29, No. 14, 22.09.2010, p. 2814-2821.

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

TY - JOUR

T1 - Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf)

T2 - Synthesis and X-ray diffraction structures of the isomeric Os3(CO) 10(bmf) clusters and HOs3(CO)8(μ-C 6H4)

AU - Kandala, Srikanth

AU - Yang, Li

AU - Campana, Charles F.

AU - Nesterov, Vladimir

AU - Wang, Xiaoping

AU - Richmond, Michael G.

PY - 2010/9/22

Y1 - 2010/9/22

N2 - The labile cluster 1,2-Os3(CO)10(MeCN)2 (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os3(CO)10(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358-383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os3(CO)10(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os3(CO)10(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs 3(CO)9(C29H23O3P 2) (3a-c). Thermolysis of HOs3(CO)9(C 29H23O3P2) (3a-c) in refluxing toluene leads to P-C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)8(μ-C6H4)(μ- C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated α to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os3(CO)10(diphosphine) derivatives prepared by our groups.

AB - The labile cluster 1,2-Os3(CO)10(MeCN)2 (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os3(CO)10(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358-383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os3(CO)10(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os3(CO)10(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs 3(CO)9(C29H23O3P 2) (3a-c). Thermolysis of HOs3(CO)9(C 29H23O3P2) (3a-c) in refluxing toluene leads to P-C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)8(μ-C6H4)(μ- C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated α to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os3(CO)10(diphosphine) derivatives prepared by our groups.

KW - Crystallography

KW - Diphosphine ligand

KW - Ligand substitution

KW - Osmium clusters

KW - P-C bond-activation

UR - https://www.scopus.com/pages/publications/77956266458

U2 - 10.1016/j.poly.2010.07.003

DO - 10.1016/j.poly.2010.07.003

M3 - Article

AN - SCOPUS:77956266458

SN - 0277-5387

VL - 29

SP - 2814

EP - 2821

JO - Polyhedron

JF - Polyhedron

IS - 14

ER -

Kandala S, Yang L, Campana CF, Nesterov V, Wang X, Richmond MG. Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5- methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P-C bond cleavage in the unsaturated cluster 1,1-Os₃(CO)₉(bmf): Synthesis and X-ray diffraction structures of the isomeric Os₃(CO) ₁₀(bmf) clusters and HOs₃(CO)₈(μ-C ₆H₄). Polyhedron. 2010 Sep 22;29(14):2814-2821. doi: 10.1016/j.poly.2010.07.003