Electrochemical generation of low-valent molybdenum tri-tertiary phosphine complexes: interactions with monophosphines and molecular nitrogen

Autor:	Colleen M. Duff-Spence, Jean Talarmin, Christopher J. Pickett, Talib I. Al-Salih, T. Adrian George, Gerald E. Bossard
Rok vydání:	1992
Předmět:	Chemistry Inorganic chemistry chemistry.chemical_element General Chemistry Electrochemistry Medicinal chemistry Chloride Ion Electron transfer chemistry.chemical_compound Molybdenum medicine Cyclic voltammetry Isomerization Phosphine medicine.drug
Zdroj:	Journal of the Chemical Society, Dalton Transactions. :2263
ISSN:	1364-5447 0300-9246
DOI:	10.1039/dt9920002263
Popis:	The electrochemical reduction of the 15-electron molybdenum(III) complex [MoCl3(dpepp)], 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 [MoCl3(dpepp)]–. Loss of chloride from this anion prior to or following further electron transfer provides two principal pathways to molybdenum(0) products, [Mo(η6-C6H5PPh2)(dpepp)] under Ar or cis-[Mo(N2)2(dpepp)(PPh3)] under molecular nitrogen, a relatively high potential pathway via molybdenum(I) solvated intermediates and a low potential pathway via trans-[MoCl2(dpepp)(PPh3)]. The cis-dinitrogen complex is unstable on the preparative time-scale, small amounts of trans-[Mo(N2)2(dpepp)(PPh3] are formed, presumably by isomerisation, but the major product is the η6-arene complex.
Databáze:	OpenAIRE
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