摘要:
Photolysis of the molybdaborane [(eta(5)-C5H5)(eta(5):eta(1)-C5H4)-arachno-2-MoB4H7] (1) in benzene-d(6) gives ca. 60% conversion to the compound [(eta(5)-C5H5)(eta(5):eta(1)-C5H4)-nido-2-MoB4H5] (2). Compound 2 could not be isolated as a solid and is thermally unstable at 20 degrees C in solution with a half-life of 3 - 4 h. Repeated photolysis and thermolysis of 1 in the presence of BH3 center dot thf gives a low yield of the known metallacarbaborane [(eta(5)-C5H5)(eta(2):eta(3)-C3H3)-Closo-1-MoC2B9H9] (3) suggesting that 3 is formed from 1 via 2. Reaction of 1 with PEt3 gives initially [(eta(5)-C5H5)(eta(5):eta(1)-C5H4)-arachno-2-MoHB4H4PEt3] (4). Longer reaction times (> 10 min, 20 degrees C) give in addition [(eta 5- C5H5)(eta(5):eta(1)-C5H4)-arachno-1-MoHB3H3PEt3] (5). Both 4 and 5 are unstable in solution or the solid state decomposing to the molybdacarbaborane [(eta(5)-C5H5)(eta(3):eta(2)-C3H3)-nido-1-MoC2B3H5] (6), [Mo(eta-C5H5)(2)H-2] and BH3 center dot PEt3. Compound 1 is deprotonated cleanly by KH in thf at the Mo - H - B bridging proton to give [(eta(5)-C5H5) (eta(5):eta(1)-C5H4)-arachno-2-MoB4H6-][K+] (7). (c) 2007 Elsevier B.V. All rights reserved.