Allylic alkylation of co-ordinated cyanide; the synthesis and X-ray crystal structure of trans-[

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Sterically encumbered charge-compensated carbaboranes: Synthesis and reactivity - Molecular structures of 7-Ph-11-SMe2-7,8-nido-C2B9H10 and 1-Ph-3,3-(CO2-7-SMe)(2)-3,1,2-closo-RhC2B9H8

Reaction between K[7-Ph-7,8-nido-C2B9H11] and dmso in H2SO4 affords a mixture of the isomers 7-Ph-9-SMe2-7,8-nido-C2B9H10 (1a) and 7-Ph-11-SMe2-7,8-nido-C2B9H10 (1b). Similarly, starting from K[7,8-Ph2-7,8-nido-C2B9H10], the diphenyl analogue 7,8-Ph2-9-SMe2-7,8-nido-C2B9H9 (2) was produced. These three new nido carbaboranes have been characterised spectroscopically, including 11B-11B COSY and 1H-1H NOESY experiments, and by a single crystal diffraction study on 1b. Deprotonation of 1a followed by addition of [RhCl(CO)2]2 affords the carbametallaborane 1-Ph-33-(CO)2-7-SMe2-3,1,2-closo-RhC2B9H9 (3), characterised by IR and 1H and 11B NMR spectroscopies and by a crystallographic study. © 1997 Elsevier Science S.A

Charge-compensated carbarhodaboranes. Synthesis and molecular structures of 3-L-3,3-(I)(2)-4-SMe2-3,1,2-closo-RhC2B9H10, L = CO or PPh3

Reaction of 3,3- (CO) 2-4-SMe2-3,1,2-closo-RhC2B9H 10 with iodine results in the formation of 3- (CO) -3,3- (I) 2-4-SMe2-3,1,2-closo-RhC2B9H 10, 1. Reaction between 1 and PPh3 results in substitution of the carbonyl group to afford 3-PPh3-3,3- (I) 2-4-SMe2-3,1,2-closo-RhC2B9H 10, 2. Both new compounds have been fully characterised by multinuclear NMR spectroscopy and also by a single crystal X-ray diffraction studies