Cupracarboranes Containing a closo-Cu(I)C2B9 Geometry. Synthesis and Structure of ((PPh3)CuC2B9H11)- and ((PPH3)2Cu2(micro-H)2C2B9H9).
CALIFORNIA UNIV LOS ANGELES DEPT OF CHEMISTRY AND BIOCHEMISTRY
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The reaction chemistry of NIDO-7,8-Carborane2- with copper I has been examined to provide anaerobic synthetic routes to two novel Phosphinocupracarboranes, PPh3CuC2B9H11- and PPh32Cu2mu-H2C2B9H9 d superscript 10. The structural analysis reveals that both cupracarboranes adopt a closo geometry for the d superscript 10 MC2B9 icosahedra. Two copper I centers of the homodi-nuclear complex are incorporated into one carboane cage via the open pentagonal C2B3 face and two B-H-Cu bridges. Both bridging BH units stem from the upper pentagonal belt resulting in the interatomic CuI-CuI distance of 2.5761 A. The relatively close CuI-CuI proximity can be ascribed to a metal-metal interaction and the dinuclear cupracarborane can be viewed as a zwitterionic salt which upon dissolution remains intact while exhibiting fluxional behavior. The nature of these fluxional processes has been explored by variable temperature multinuclear FTNMR spectroscopy. Keywords Crystallization.
- Organic Chemistry