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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(N2C10H6-6-R)

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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 HOs3(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(N2C10H6-6-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-6′ ortho 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 HOs3(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.

Graphical Abstract

The reaction between the labile cluster Os3(CO)10(MeCN)2 (1) and the monofunctionalized heterocyclic ligand 6-Et-2,2′-bipyridine proceeds readily at room temperature to furnish an isomeric mixture of the cyclometalated and ortho-metalated hydride-bridged clusters HOs3(CO)9(N2C12H11) (2 and 3). Treatment of 1 with 6-Ph-2,2′-bipyridine also yields two distinct hydride-containing clusters that result from independent ortho-metalation paths involving the 6-phenyl substituent and unsubstituted bipyridine group. The bipyridine-derived ortho metalation attendant in the new clusters HOs3(CO)9(N2C10H6-6-Et) (3) and HOs3(CO)9(N2C10H6-6-Ph) (5) has been established by X-ray crystallography.

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Scheme 1
Fig. 1

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Notes

  1. While the four bipyridine-substituted clusters 2–5 were subjected to mass spectrometric investigation, 2–4 were unstable and decomposed during sample preparation or in the mass spectrometer. Only 5 afforded meaningful mass spectral data.

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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.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, San Diego State University, San Diego, CA, 82182, USA

    Carl J. Carrano

  2. Neutron Scattering Science Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA

    Xiaoping Wang

  3. Department of Chemistry, University of North Texas, Denton, TX, 76203, USA

    Bhaskar Poola & Michael G. Richmond

  4. Department of Chemistry, Abilene Christian University, Abilene, TX, 79699, USA

    Cynthia B. Powell

Authors
  1. Carl J. Carrano
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  2. Xiaoping Wang
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  3. Bhaskar Poola
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  4. Cynthia B. Powell
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  5. Michael G. Richmond
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Corresponding authors

Correspondence to Xiaoping Wang or Michael G. Richmond.

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Carrano, C.J., Wang, X., Poola, B. et al. 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(N2C10H6-6-R). J Chem Crystallogr 39, 820–826 (2009). https://doi.org/10.1007/s10870-009-9574-4

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