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Martin Zanni, E. D. Jemmis, Sankarampadi Aravamudhan, Elangannan Arunan, Neil Hunt, Sanghamitra Mukhopadhyay, Helena J. Shepherd, Srihari Keshavamurthy, Arend G. Dijkstra, Mike Ashfold, Himangshu Prabal Goswami, Artur Nenov, Himani Medhi, Kenneth Ghiggino, Kiran Moirangthem, R. J. Dwayne Miller, Debabrata Goswami, Siva Umapathy, John R. Helliwell, Jonathan D. Hirst, Stephen Meech, Shaul Mukamel, Biman Bagchi and Marylise Buron-Le Cointe

E. D. Jemmis, Sankarampadi Aravamudhan, Elangannan Arunan, Abhishek Shahi, Neil Hunt, Christoph Schnedermann, John R. Helliwell, Mike Ashfold, Himangshu Prabal Goswami, Artur Nenov, Volker Deckert, Priyadarshi Roy Chowdhury, Kenneth Ghiggino, R. J. Dwayne Miller, Debabrata Goswami, Wolfgang Junge, Judith Howard, Keisuke Tominaga, Tim Brandt van Driel, Martin Zanni, Siva Umapathy, Martin Meedom Nielsen, R. Pal and Shaul Mukamel

Theoretical Study of the Electronic Structure and Reactions of R2W (μ-CR)2 WR2

Pyrolysis of (eta(5)-C(5)Me(5)WH(3))B(4)H(8), 1, in the presence of excess BHCl(2) x SMe(2) in toluene at 100 degrees C led to the isolation of (eta(5)-C(5)Me(5)W)(2)B(5)H(9), 2, and B-Cl inserted (eta(5)-C(5)Me(5)W)(2)B(5)H(8)Cl, 3, and (eta(5)-C(5)Me(5)W)(2)B(5)H(7)Cl(2), 4-7 (four isomers). All the chlorinated tungstaboranes were isolated as red and air and moisture sensitive solids. These new compounds have been characterized in solution by (1)H, (11)B, (13)C NMR, and the structural types were unequivocally established by crystallographic analysis of compounds 3, 4, and 7. Density functional theory (DFT) calculations were carried out on the model molecules of 3-7 to elucidate the actual electronic structures of these chlorinated species. On grounds of DFT calculations we demonstrated the role of transition metals, bridging hydrogens, and the effect of electrophilic substitution of hydrogens at B-H vertices of metallaborane structures.

Empirical force field calculations indicate that1c,2c and3c rather than1a,2a and3a are more favourable precursors for photocycloadditions to give [5]-, [6]- and [7]-prismane respectively.