Abstract
Abstract Separate series of neutral and anionic osmium carbonyl clusters based on 3–20 osmium atoms have been prepared and characterised in the solid by single crystal X-ray analysis and in solution largely by 13 C NMR spectroscopy and vibrational analysis (IR). They appear to fall into two distinct series, viz ., those which follow a polytetrahedral, non-metallic growth sequence, e.g. [Os 3 (CO) 12 ] and [Os 3 (CO) 11 ] 2− , [Os 4 (CO) 14 ] and [Os 4 (CO) 13 ] 2− , [Os 5 (CO) 16 ] and [Os 5 (CO) 15 ] 2− , and [Os 6 (CO) 18 ] and [Os 6 (CO) 17 ] 2− , and those which apparently follow the route to bcc packing, e.g. [Os 6 (CO) 18 ] 2− , [Os 7 (CO) 21 ] and [Os 7 (CO) 20 ] 2− , [Os 8 (CO) 23 ] and [Os 8 (CO) 22 ] 2− , [Os 9 (CO) 24 ] 2− , [Os 10 (CO) 26 ] 2− and [Os 10 C(CO) 24 ] 2− , and [Os 20 (CO) 40 ] 2− . Alternatively, the species [Os 4 (CO) 14 ] and [Os 4 (CO) 13 ] 2− , [Os 10 (CO) 26 ] 2− and [Os 10 C(CO) 24 ] 2− and [Os 20 (CO) 40 ] 2− may be viewed as forming a ‘magic number’ sequence of clusters corresponding to the tetrahedral growth pattern, viz . 4, 10, and 20. Also described are the syntheses of mixed Os-C and Os-Hg clusters. The former bear a close resemblance to the carboranes in their structural features, whereas the Os-Hg clusters represent examples of linked cluster systems containing both transition metal and main group cluster domains. The geometric relevance that all these structures bear to the ‘metallic state’ is discussed.
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