Electrochemical Generation of Low-valent Molybdenum Tri-tertiary Phosphine Complexes: Interactions with Monophosphines and Molecular Nitrogen

DOI: 10.1039/DT9920002263

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2263 - 2270 (1992)

Update date:2022-07-30

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Authors:

Talarmin, Jean

Al-Salih, Talib I.

Pickett, Christopher J.

Bossard, Gerald E.

George, T. Adrian

Duff-Spence, Colleen M.

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Article abstract of DOI:10.1039/DT9920002263

The electrochemical reduction of the 15-electron molybdenum(III) complex , dpepp = Ph2PCH2CH2P(Ph)CH2CH2PPh2, has been studied in the presence of PPh3 under argon and under molecular nitrogen.The primary reduction of the trichloride involves a reversible single-electron transfer to give the unstable 16-electron molybdenum(II) anion -.Loss of chloride from this anion prior to or following further electron transfer provides two principal pathways to molybdenum(0) products, 6-C6H5PPh2)(dpepp)> under Ar or cis- under molecular nitrogen, a relatively high potential via molybdenum(I) solvated intermediates and a low potential pathway via trans-.The cis-dinitrogen complex is unstable on the preparative timescale, small amounts of trans- are formed, presumably by isomerisation, but the major product is the η⁶-arene complex.

Full text of DOI:10.1039/DT9920002263

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