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Synthesis and Structural Characterization of Copper(I) Cupracarboranes. A Novel 'Pinwheel' Cluster

机译：铜（I）铜硼烷的合成与结构表征。一种新颖的“风车”集群

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The polyhedral CuC2B9 framework is a common structural feature displayed by all four cupracarboranes. The geometry of this cage framework varies in such a way that opening of the (d10-M)C2B9 icosahedra increases in the order of 3,4,5 and 6, resulting in closo geometry for 3 and 4, nido geometry for 6, and an intermediate geometry for 5. Two copper(I) centers in 4 are associated with one carborane cage via the open pentagonal C2B3 face and two B-H-Cu bridges. Both bridging BH units originate from the upper pentagonal belt of the dicarbollide moiety, resulting in an interatomic Cu(I)-Cu(I) distance of 2.576(1) Angstroms. In a formal sense, 4 is a zwitterion composed of an anionic 3 complexed with a Cu(PPh3)+ cation. The dinuclear structural integrity of 4 remains intact upon dissolution, although fluxional processes become operative, as revealed by variable temperature multinuclei FT NMR spectroscopy. THe trinuclear cupracarborane 6 contains three CuC2B9H10(4-(C5H4N)CO2CH3) units, which are linked by both Cu-H-B and Cu-Cu (2.519(2) Angstroms) interactions about a crystallographic 3-fold axis such that a pinwheel ligand array around an equilateral Cu3 core results. Compound 6 represents an example of a clustered cluster . The extent of metal-metal interactions in 4 and 6, as implied by their relatively short copper-copper distances, is discussed. Structural comparison of these copper(I) complexes suggests that the substituent at boron is not electronically innocent with respect to molecular distortions. Reprints. (jes)

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