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The Impact of Weak CH⋅⋅⋅Rh Interactions on the Structure and Reactivity of trans ‐[Rh(CO) 2 (phosphine) 2 ] + : An Experimental and Theoretical Examination
Author(s) -
Montag Michael,
Efremenko Irena,
Cohen Revital,
Leitus Gregory,
Shimon Linda J. W.,
DiskinPosner Yael,
BenDavid Yehoshoa,
Martin Jan M. L.,
Milstein David
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801171
Subject(s) - phosphine , reactivity (psychology) , rhodium , chemistry , physics , catalysis , organic chemistry , medicine , alternative medicine , pathology
The crystal structure of the new cationic Rh I complex trans ‐[Rh(CO) 2 (L) 2 ]BF 4 (L=α 2 ‐(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OCRhCO fragment and weak intramolecular CH⋅⋅⋅Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OCRhCO fragment. This linkage has also been demonstrated by comparison with a highly similar Rh I complex, in which these CH⋅⋅⋅Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.