α-Diimine ligand coordination and C-H bond activation in the reaction of Os3(CO)10(MeCN)2 with 6-R-2,2-Bipyridine (where R = Et, Ph): X-ray diffraction structures of the ortho-metalated hydride clusters HOs3(CO)9(N2C10H 6-6-R)

Carl J. Carrano; Xiaoping Wang; Bhaskar Poola; Cynthia B. Powell; Michael G. Richmond

doi:10.1007/s10870-009-9574-4

α-Diimine ligand coordination and C-H bond activation in the reaction of Os₃(CO)₁₀(MeCN)₂ with 6-R-2,2-Bipyridine (where R = Et, Ph): X-ray diffraction structures of the ortho-metalated hydride clusters HOs₃(CO)₉(N₂C₁₀H ₆-6-R)

Carl J. Carrano, Xiaoping Wang, Bhaskar Poola, Cynthia B. Powell, Michael G. Richmond

Single Crystal Diffraction

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

2 Scopus citations

Abstract

The reactivity of the labile cluster Os₃(CO)₁₀(MeCN) ₂ (1) with the monofunctionalized heterocyclic ligands 6-R-2,2-bipyridine (where R = Et, Ph) has been investigated. The alkyl-substituted heterocycle 6-Et-2,2-bipyridine reacts with 1 in refluxing CH₂Cl₂ to give an isomeric mixture of HOs ₃(CO)₉(N₂C₁₂H₁₁) due to cyclometalation of the side-chain ethyl group (2) and ortho metalation of the unsubstituted bipyridine ring (3). The solid-state structure of the latter cluster, HOs₃(CO)₉(N₂C₁₀H ₆-6-Et) (3), has unequivocally established the site of the C-H bond activation in the product. Treatment of 1 with the aryl-substituted ligand 6-Ph-2,2-bipyridine proceeds similarly with ortho metalation at the ancillary phenyl group and the C-6ortho site of the unsubstituted bipyridine ring, as verified by ¹H NMR spectroscopy. The X-ray diffraction structure of the thermodynamically more stable bipyridine-metalated cluster HOs ₃(CO)₉(N₂C₁₀H₆-6-Ph) (5) has been determined. The course of these reactions is discussed with respect to our recent study involving the reaction of cluster 1 with the ligand 6-Me-2,2-bipyridine.

Original language	English
Pages (from-to)	820-826
Number of pages	7
Journal	Journal of Chemical Crystallography
Volume	39
Issue number	11
DOIs	https://doi.org/10.1007/s10870-009-9574-4
State	Published - 2009

Funding

Acknowledgments Financial support from the NSF (CJC) and Robert A. Welch Foundation (Grant B-1093-MGR) is greatly appreciated. The NSF-MRI program grant CHE-0320848 is gratefully acknowledged for support of the X-ray diffraction facilities at San Diego State University. We also acknowledge the expert assistance of Dr. Yongxuan Su and his recording the mass spectrum for cluster 5.

Keywords

Cyclometalation
Ligand substitution
Ortho metalation
Triosmium clusters
α-Diimine ligand

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Carrano, C. J., Wang, X., Poola, B., Powell, C. B., & Richmond, M. G. (2009). α-Diimine ligand coordination and C-H bond activation in the reaction of Os₃(CO)₁₀(MeCN)₂ with 6-R-2,2-Bipyridine (where R = Et, Ph): X-ray diffraction structures of the ortho-metalated hydride clusters HOs₃(CO)₉(N₂C₁₀H ₆-6-R). Journal of Chemical Crystallography, 39(11), 820-826. https://doi.org/10.1007/s10870-009-9574-4

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title = "α-Diimine ligand coordination and C-H bond activation in the reaction of Os3(CO)10(MeCN)2 with 6-R-2,2-Bipyridine (where R = Et, Ph): X-ray diffraction structures of the ortho-metalated hydride clusters HOs3(CO)9(N2C10H 6-6-R)",

abstract = "The reactivity of the labile cluster Os3(CO)10(MeCN) 2 (1) with the monofunctionalized heterocyclic ligands 6-R-2,2-bipyridine (where R = Et, Ph) has been investigated. The alkyl-substituted heterocycle 6-Et-2,2-bipyridine reacts with 1 in refluxing CH2Cl2 to give an isomeric mixture of HOs 3(CO)9(N2C12H11) due to cyclometalation of the side-chain ethyl group (2) and ortho metalation of the unsubstituted bipyridine ring (3). The solid-state structure of the latter cluster, HOs3(CO)9(N2C10H 6-6-Et) (3), has unequivocally established the site of the C-H bond activation in the product. Treatment of 1 with the aryl-substituted ligand 6-Ph-2,2-bipyridine proceeds similarly with ortho metalation at the ancillary phenyl group and the C-6ortho site of the unsubstituted bipyridine ring, as verified by 1H NMR spectroscopy. The X-ray diffraction structure of the thermodynamically more stable bipyridine-metalated cluster HOs 3(CO)9(N2C10H6-6-Ph) (5) has been determined. The course of these reactions is discussed with respect to our recent study involving the reaction of cluster 1 with the ligand 6-Me-2,2-bipyridine.",

keywords = "Cyclometalation, Ligand substitution, Ortho metalation, Triosmium clusters, α-Diimine ligand",

author = "Carrano, {Carl J.} and Xiaoping Wang and Bhaskar Poola and Powell, {Cynthia B.} and Richmond, {Michael G.}",

year = "2009",

doi = "10.1007/s10870-009-9574-4",

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Carrano, CJ, Wang, X, Poola, B, Powell, CB & Richmond, MG 2009, 'α-Diimine ligand coordination and C-H bond activation in the reaction of Os₃(CO)₁₀(MeCN)₂ with 6-R-2,2-Bipyridine (where R = Et, Ph): X-ray diffraction structures of the ortho-metalated hydride clusters HOs₃(CO)₉(N₂C₁₀H ₆-6-R)', Journal of Chemical Crystallography, vol. 39, no. 11, pp. 820-826. https://doi.org/10.1007/s10870-009-9574-4

α-Diimine ligand coordination and C-H bond activation in the reaction of Os₃(CO)₁₀(MeCN)₂ with 6-R-2,2-Bipyridine (where R = Et, Ph): X-ray diffraction structures of the ortho-metalated hydride clusters HOs₃(CO)₉(N₂C₁₀H ₆-6-R). / Carrano, Carl J.; Wang, Xiaoping; Poola, Bhaskar et al.
In: Journal of Chemical Crystallography, Vol. 39, No. 11, 2009, p. 820-826.

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

TY - JOUR

T1 - α-Diimine ligand coordination and C-H bond activation in the reaction of Os3(CO)10(MeCN)2 with 6-R-2,2-Bipyridine (where R = Et, Ph)

T2 - X-ray diffraction structures of the ortho-metalated hydride clusters HOs3(CO)9(N2C10H 6-6-R)

AU - Carrano, Carl J.

AU - Wang, Xiaoping

AU - Poola, Bhaskar

AU - Powell, Cynthia B.

AU - Richmond, Michael G.

PY - 2009

Y1 - 2009

N2 - The reactivity of the labile cluster Os3(CO)10(MeCN) 2 (1) with the monofunctionalized heterocyclic ligands 6-R-2,2-bipyridine (where R = Et, Ph) has been investigated. The alkyl-substituted heterocycle 6-Et-2,2-bipyridine reacts with 1 in refluxing CH2Cl2 to give an isomeric mixture of HOs 3(CO)9(N2C12H11) due to cyclometalation of the side-chain ethyl group (2) and ortho metalation of the unsubstituted bipyridine ring (3). The solid-state structure of the latter cluster, HOs3(CO)9(N2C10H 6-6-Et) (3), has unequivocally established the site of the C-H bond activation in the product. Treatment of 1 with the aryl-substituted ligand 6-Ph-2,2-bipyridine proceeds similarly with ortho metalation at the ancillary phenyl group and the C-6ortho site of the unsubstituted bipyridine ring, as verified by 1H NMR spectroscopy. The X-ray diffraction structure of the thermodynamically more stable bipyridine-metalated cluster HOs 3(CO)9(N2C10H6-6-Ph) (5) has been determined. The course of these reactions is discussed with respect to our recent study involving the reaction of cluster 1 with the ligand 6-Me-2,2-bipyridine.

AB - The reactivity of the labile cluster Os3(CO)10(MeCN) 2 (1) with the monofunctionalized heterocyclic ligands 6-R-2,2-bipyridine (where R = Et, Ph) has been investigated. The alkyl-substituted heterocycle 6-Et-2,2-bipyridine reacts with 1 in refluxing CH2Cl2 to give an isomeric mixture of HOs 3(CO)9(N2C12H11) due to cyclometalation of the side-chain ethyl group (2) and ortho metalation of the unsubstituted bipyridine ring (3). The solid-state structure of the latter cluster, HOs3(CO)9(N2C10H 6-6-Et) (3), has unequivocally established the site of the C-H bond activation in the product. Treatment of 1 with the aryl-substituted ligand 6-Ph-2,2-bipyridine proceeds similarly with ortho metalation at the ancillary phenyl group and the C-6ortho site of the unsubstituted bipyridine ring, as verified by 1H NMR spectroscopy. The X-ray diffraction structure of the thermodynamically more stable bipyridine-metalated cluster HOs 3(CO)9(N2C10H6-6-Ph) (5) has been determined. The course of these reactions is discussed with respect to our recent study involving the reaction of cluster 1 with the ligand 6-Me-2,2-bipyridine.

KW - Cyclometalation

KW - Ligand substitution

KW - Ortho metalation

KW - Triosmium clusters

KW - α-Diimine ligand

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U2 - 10.1007/s10870-009-9574-4

DO - 10.1007/s10870-009-9574-4

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Carrano CJ, Wang X, Poola B, Powell CB, Richmond MG. α-Diimine ligand coordination and C-H bond activation in the reaction of Os₃(CO)₁₀(MeCN)₂ with 6-R-2,2-Bipyridine (where R = Et, Ph): X-ray diffraction structures of the ortho-metalated hydride clusters HOs₃(CO)₉(N₂C₁₀H ₆-6-R). Journal of Chemical Crystallography. 2009;39(11):820-826. doi: 10.1007/s10870-009-9574-4