期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：1978
卷号：75
期号：3
页码：1056-1059
DOI：10.1073/pnas.75.3.1056
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：A simple synthesis of the zerovalent complex Mo[P(OCH3)3]6 has been devised from a potassium reduction of MoCl4(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(OCH3)3]6+. The major product was an octahedral nonhydridic cation, Mo[P(OCH3)3]5P(OCH3)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(OCH3)3]5P(OCH3)2+-PF6-. Extended reaction of trifluoroactic acid with Mo[P(OCH3)3]6 yielded the seven-coordinate hydride, HMo[P(OCH3)3]4(O2CCF3), which was near pentagonal bipyramidal and was stereochemically nonrigid.
关键词：phosphite ester cleavage ; intramolecular methoxy group exchange
