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Theoretical study of structure and NMR properties of the μ‐hydrido‐bridged cyclodecyl cation and related systems
Author(s) -
Galasso V.
Publication year - 1998
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1998)70:2<313::aid-qua7>3.0.co;2-x
Subject(s) - chemistry , computational chemistry , crystallography , chemical physics
Full conformational analysis on the cyclodecyl cation was performed at the HF/6‐31G** level of theory. The most stable conformer is established as having a boat–chair structure with a 1,5‐transannular interaction and a symmetrical and bent μ‐hydrido bridge, which involves a two‐electron three‐center bond. Similar boat–chair conformations are preferred by the homologous cyclooctyl and cyclononyl cations. For the related diaza‐ and diboracyclodecyl ions, the 1,6‐transannular interaction in a cis ‐decalin‐type geometry is more favorable than is the competing 1,5‐process. These structural models are fully consistent with the main features observed in the NMR spectra. In particular, the unusual patterns of the chemical shifts and nuclear spin–spin coupling constants in the bridging backbones H t X(DOTTED BOND)H μ (DOTTED BOND)XH t are also satisfactorily reproduced by the ab initio results obtained with the continuous‐set‐of‐gauge‐transformations and equations‐of‐motion methods, respectively. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 313–320, 1998