Synthesis of the cluster dianion [Os11C(CO)27]2–by pyrolysis and its reactions with electrophiles; X-ray structure analysis of the mixed-metal derivative [PMePh3][Os11C(CO)27{Cu(NCMe)}]·CH2Cl2and the hydrido derivative [PMePh3][Os11C(CO)27H]
- 1 January 1989
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 8,p. 1455-1464
- https://doi.org/10.1039/dt9890001455
Abstract
The new cluster species [Os11C(CO)27]2–(2) has been identified as one of the products resulting from the pyrolysis of [Os3(CO)12]. It reacts with [Cu(NCMe)4] BF4 to yield the monoanion [Os11C(CO)27{Cu(NCMe)}]–(4) and [Os11C(CO)27{Cu(NCMe)}2](5). The reaction of (2) with iodine-iodide produces a series of iodo-clusters [Os11C(CO)27I]–(8) and [Os11C(CO)27I2](9) which are converted back into (2) by addition of halide ions. The unstable monoanionic species [Os11C(CO)27{M(PMe2Ph)}]–[M = Au (3) or Cu (7)] are obtained on reaction of (2) with [M(PMe2Ph)]+, and further reaction of (3) yields [Os11C(CO)27{Au(PMe2Ph)}2](6). The dianionic cluster (2) reacts with acid to give the monoanion [Os11C(CO)27H]–(10) and [Os11C(CO)27H2](11). The reaction with Hg(C6Cl5)(O2CCF3) yields initially the unstable monoanion [Os11C(CO)27{Hg(C6Cl5)}]–(12) which is rapidly converted into the known cluster dianion [Os20Hg(C)2(CO)48]2–. X-Ray analysis of the [PMePh3]+ salts of (4) and (10) reveal identical Os11 core geometries, but in (4) the copper ligand occupies a µ3-bridging position, while the hydride in (10) appears to be located in an interstitial site.Keywords
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