Removing a second mercury atom from [Os18Hg3C2(CO)42]2-: synthesis of [Os18HgC2(CO)42]4- and crystal structure of [PPh3H3Os18HgHC2(CO)42]

Gade, Lutz H., Johnson, Brian F. G., Lewis, Jack , McPartlin, Mary and Scowen, Ian J. (1996) Removing a second mercury atom from [Os18Hg3C2(CO)42]2-: synthesis of [Os18HgC2(CO)42]4- and crystal structure of [PPh3H3Os18HgHC2(CO)42]. Journal of the Chemical Society, Dalton Trans. (5). pp. 597-601. ISSN 1477-9226

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Upon reduction of N(PPh)OsHgC(CO)(= 2 or 3) with sodium diphenylketyl in tetrahydrofuran a hexaanionic cluster{,} OsHgC(CO){,} is generated which could only be partially characterised by IR spectroscopy as well as through its chemical reactivity. After chromatographic work-up the tetraanionic cluster OsHgC(CO) was isolated as the exclusive reaction product. This was also obtained in low yield (20-30%) by thermolytic degradation of OsHgC(CO) in CHCl. As a consequence of traces of HCl in the CHCl as well as degradation of the cation{,} the salt PPhHOsHgHC(CO) crystallised from the reaction mixture. An X-ray single-crystal analysis of the latter has established its solid-state structure in which two OsC units are small micro-linked by a central mercury atom. The OsHgC(CO) cluster may be converted into the dimercury cluster dianion OsHgC(CO) by reaction with Hg(OSCF).

Subjects:F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Chemistry
ID Code:13269
Deposited On:19 Mar 2014 17:58

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