Abstract
Clusters (R′P)(RCCR)Fe 3(CO) 9 ( 1) have a pentagonal pyramidal cage structure with a planar C 2Fe 2P cycle acting as a organometallic 4π ligand towards a side-on η 5-coordinated Fe(CO) 3 entity. Compounds of this type, which may be considered halfsandwich complexes, undergo transformation to clusters (R′P)(RCCR)Fe 4(CO) 11 ( 2) which correspond to triple-decker compounds with a planar central C 2Fe 2P 4π ligand. Compounds 2 can also be described as pentagonal bipyramidal clusters. Since compounds 1 are chemically related to a number of different cage molecules containing a C 2PFe 3 core and also to binuclear complexes with a C 2PFe 2 core, the triple-decker clusters 2 can also be prepared from these starting materials. Several examples of this type are given. The isoelectronic analogy between RP and S as cluster constituents is exemplified by the synthesis of a sulfur-containing analogue of 2 by similar procedures.
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