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1,3,2‐Diselenaborolanes with an Annelated Dicarba‐ closo ‐dodecaborane(12) Unit: Synthesis, Molecular Structure and Reactivity
Author(s) -
Wrackmeyer Bernd,
Klimkina Elena V.,
Milius Wolfgang
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100563
Subject(s) - chemistry , yield (engineering) , reactivity (psychology) , boron , nuclear magnetic resonance spectroscopy , carborane , crystallography , fluoride , coupling constant , derivative (finance) , computational chemistry , medicinal chemistry , stereochemistry , inorganic chemistry , organic chemistry , medicine , physics , particle physics , materials science , alternative medicine , pathology , economics , financial economics , metallurgy
Exchange reactions of 2,2‐dimethyl‐1,3‐diselena‐2‐silacyclopentane and 2,2,3,3‐tetramethyl‐1,4‐diselena‐2,3‐disilacyclohexane, as the 4,5‐ and 5,6‐[1,2‐dicarba‐ closo ‐dodecaborano(12)] derivatives, respectively, with boron trihalides (BCl 3 , BBr 3 , BI 3 ) and dichlorides (PhBCl 2 , i Pr 2 NBCl 2 ) afford the corresponding 1,3,2‐diselenaborolanes in essentially quantitative yield. The products were characterized in solution by multinuclear magnetic resonance spectroscopy ( 1 H, 11 B, 13 C, 29 Si, 77 Se), and for two products, in the solid state by X‐ray structural analysis. Attempts to synthesize the boron fluoride failed, and the methoxy derivative was obtained in a mixture with a decomposition product. The gas‐phase structures of all relevant products were optimized by DFT hybrid methods [RB3LYP/6‐311+G(d.p) level of theory], and NMR parameters (shielding constants and spin–spin coupling constants) were calculated. The calculated data compare well with experimental data, both for the structures and the NMR spectroscopic parameters.