The chemistry of metal carbonyl anions. II. Synthesis and reactions of the pentacarbonylmetallate dianions of chromium, molybdenum, and tungsten with metallic monohalides

John E. Ellis, Steven G. Hentges, Dale G. Kalina, Gary P. Hagen

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Abstract

Alkali metal amalgam reductions of M(CO)6 in tetrahydrofuran (THF) have provided salts of the pentacarbonylmetallate dianions. Cesium amalgam reacts with M(CO)6 at room temperature to yield Cs2M(CO)5, while sodium or potassium amalgams provide only (Na or K)2Cr(CO)5 in good yield in addition to a substantial amount of (Na or K)2Cr2(CO)10. Molybdenum and tungsten carbonyl give primarily (Na or K)2M2(CO)10 in THF even after 24 h of reflux; however, infrared evidence indicates the presence of monomeric dianions in these solutions. Reaction of the monomeric dianions with Ph3MCl (M = Ge, Sn, Pb) provides air- and moisture-stable substituted carbonyl anions of the type Ph3MM′(CO)5- (M′ = Cr, Mo, W) which have been isolated as tetraethylammonium salts. Pure Na2Cr(CO)5, prepared from the interaction of Cr(CO)6 with sodium metal in liquid ammonia or HMPA, has also been used to provide similar substituted carbonyl anions of the type ECr(CO)5- where E = Me3Sn and C5H5Fe(CO)2. The triphenyltin derivatives have also been prepared independently by the interaction of Ph3SnLi with M′(CO)6 in THF at room temperature as well as from the reaction of Ph3SnCl with M′2(CO)102- in THF.

Original languageEnglish (US)
Pages (from-to)79-93
Number of pages15
JournalJournal of Organometallic Chemistry
Volume97
Issue number1
DOIs
StatePublished - Sep 9 1975

Bibliographical note

Funding Information:
The authors express their appreciation to the donors of the Petroleum Research Fund (PRF 2670-G3), administered by the American Chemical Society, the University of Minnesota Graduate School, and the NSF-Undergraduate Research Participation Program for partial support of this work.

Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.

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