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A Novel Bis(phosphido)pyridine [PNP]2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexes

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Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, United States, and King Fahd University of Petroleum & Minerals, P.O. Box 5069, Dhahran 31261, Saudi Arabia
*To whom correspondence should be addressed. E-mail: [email protected]
Cite this: Organometallics 2010, 29, 23, 6408–6416
Publication Date (Web):November 3, 2010
Copyright © 2010 American Chemical Society

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    Abstract Image

    A novel PNP bis(secondary phosphine)pyridine pincer ligand, 2,6-bis(2-(phenylphosphino)phenyl)pyridine, has been prepared in high yield, and the properties of the doubly deprotonated form as a ligand in K4(PNP)2(THF)6 and (PNP)Zr(NMe2)2 have been investigated. The neutral PNP ligand has been isolated as a mixture of noninterconverting diastereomers, due to the presence of two chirogenic phosphorus atoms of the secondary phopshines, but coordination of the dianionic form to potassium and zirconium allows for isolation of a single diastereomer in near-quantitative yield. The structure of a bis(dimethylamido)zirconium(IV) derivative of the bis(phosphido)pyridine ligand and DFT calculations suggest that the phosphides do not π-bond to early transition metals, likely due to geometric strain and possibly orbital size mismatch between phosphorus and zirconium. As a result, the soft phosphides are prone to formation of insoluble oligomers with substantial bridging of the phosphido lone pairs to other zirconium centers.

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    Figures giving NMR spectra for all compounds and tables and CIF files giving X-ray crystallographic data data for dimeric 12 and 13. This material is available free of charge via the Internet at Crystallographic data have also been deposited at the CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K., and copies can be obtained on request, free of charge, by quoting the publication citation and the deposition numbers 787542 and 787543.

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