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Muetterties EL, Kirner JF, Evans WJ, et al. Chemistry of low-valent molybdenum phosphite complexes: Models of seven-coordinate reaction intermediates. Proc Natl Acad Sci U S A. 1978;75(3):1056-9doi: 10.1073/pnas.75.3.1056.
Muetterties, E. L., Kirner, J. F., Evans, W. J., Watson, P. L., Abdel-Meguid, S., Tavanaiepour, I., & Day, V. W. (1978). Chemistry of low-valent molybdenum phosphite complexes: Models of seven-coordinate reaction intermediates. Proceedings of the National Academy of Sciences of the United States of America, 75(3), 1056-9. https://doi.org/10.1073/pnas.75.3.1056
Muetterties, E L, et al. "Chemistry of low-valent molybdenum phosphite complexes: Models of seven-coordinate reaction intermediates." Proceedings of the National Academy of Sciences of the United States of America vol. 75,3 (1978): 1056-9. doi: https://doi.org/10.1073/pnas.75.3.1056
Muetterties EL, Kirner JF, Evans WJ, Watson PL, Abdel-Meguid S, Tavanaiepour I, Day VW. Chemistry of low-valent molybdenum phosphite complexes: Models of seven-coordinate reaction intermediates. Proc Natl Acad Sci U S A. 1978 Mar;75(3):1056-9. doi: 10.1073/pnas.75.3.1056. PMID: 16592505; PMCID: PMC411405.
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Proc Natl Acad Sci U S A. 1978 Mar;75(3):1056-9. doi: 10.1073/pnas.75.3.1056.

Chemistry of low-valent molybdenum phosphite complexes: Models of seven-coordinate reaction intermediates.

Proceedings of the National Academy of Sciences of the United States of America

E L Muetterties, J F Kirner, W J Evans, P L Watson, S Abdel-Meguid, I Tavanaiepour, V W Day

Affiliations

  1. Department of Chemistry, Cornell University, Ithaca, New York 14853.

PMID: 16592505 PMCID: PMC411405 DOI: 10.1073/pnas.75.3.1056

Abstract

A simple synthesis of the zerovalent complex Mo[P(OCH(3))(3)](6) has been devised from a potassium reduction of MoCl(4)(tetrahydrofuran)(2) followed by reaction with trimethyl phosphite at 70 degrees . Protonation of this octahedral complex gave only low yields of the expected seven-coordinate hydride, HMo[P(OCH(3))(3)](6) (+). The major product was an octahedral nonhydridic cation, Mo[P(OCH(3))(3)](5)P(OCH(3))(2) (+), derived from proton cleavage of the P-O phosphite ester bond. This octahedral cation was stereochemically nonrigid, apparently through facile methoxy group migration. Close packing by methoxy groups in this fluxional cation was established through an x-ray crystallographic study of Mo[P(OCH(3))(3)](5)P(OCH(3))(2) (+)-PF(6) (-). Extended reaction of trifluoroactic acid with Mo[P(OCH(3))(3)](6) yielded the seven-coordinate hydride, HMo[P(OCH(3))(3)](4)(O(2)CCF(3)), which was near pentagonal bipyramidal and was stereochemically nonrigid.

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