1422360-46-0Relevant academic research and scientific papers
Angular distortions at benzylic carbons due to intramolecular polarization-induced metal-arene interactions: A case study with open-shell chromium(II) NHC complexes
Danopoulos, Andreas A.,Monakhov, Kirill Yu.,Robert, Vincent,Braunstein, Pierre,Pattacini, Roberto,Conde-Guadano, Susana,Hanton, Martin,Tooze, Robert P.
, p. 1842 - 1850 (2013)
The synthesis and full characterization of the unprecedented open-shell Cr(II) benzyl organometallic complexes [Cr(NHC)2(benzyl)2] (2) and [Cr(NHC*)(benzyl)2] (3) (NHC = N,N′- diisopropylimidazol-2-ylidene; NHC* = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene) from [Cr(benzyl)3(THF) 3] and [CrCl2(THF)2]/[Mg(benzyl)2], respectively, uncovered unusually acute angles (93 in 2 and 76 in 3) at the sp3 benzylic C of the coordinated benzyl ligands. Detailed theoretical analyses (DFT and CASPT2) of the four-and three-coordinate Cr(II) species were performed to elucidate the physical origin of the benzyl bending and led to the recognition of a noncovalent, intramolecular polarization-induced metal-arene (PIMA) interaction as being responsible for it. The energetic contribution from a single PIMA interaction is estimated to be ca. 50 kJ/mol. A comparison with the origin of the angular distortions in the d0 [Zr(benzyl)4] complex will also be presented. Sharing the common origin of an induced-dipole charge density scheme with intermolecular anion-π interactions, the intramolecular PIMA interaction concept involving a transition metal unpaired d electron and arene-π orbitals can be viewed as an extension of intermolecular anion-π interactions and leads to remarkable quantitative prediction of the observed structural distortions. PIMA interactions may manifest themselves in diverse structural and dynamic phenomena and have broad implications in chemical sciences.
