The truth is out there: the metal-π interactions in crystal of Cr(CO)3(pcp) as revealed by the study of vibrational smearing of electron density

Abstract

Abstract The vibrational smearing of electron density was studied in the crystal of complex of Cr(CO)3 with [2.2]paracyclophane. The combination of theoretical and experimental methods, including periodic calculations and screening of DFT calculated and multipole-decomposed electron densities, was utilized to reveal the vibrational smearing of electron density and its influence on the multipole-constructed electron density. The multipole model, commonly used to treat the high-resolution X-ray diffraction data, was shown to be rather inaccurate in description of electron density and its vibrational smearing in metal-π complex where the interchange between diatomic interactions can occur. Namely, some bond critical points can be hidden while analyzing multipole-decomposed electron density with proved effects of vibrational smearing even if the deconvolution problem is overcome by using the invariom approach. On the contrary, the recently proposed “clouds of critical point variation” (CCPV) approach is demonstrated as the route to gather all reasonable bonding trends and to reconstruct static electron density pattern in metal-π complexes.