Non-covalent Stabilization in Transition Metal Coordination and Organometallic Complexes
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Non-covalent interactions (NCIs) are ubiquitous in nature, and the demonstration of their role in transition metal chemistry remains a vivid domain of research. Indeed, a better understanding of the interplay of NCIs with covalent interactions remains critical as it may create the basis for new conceptual frameworks for the engineering of new functional organometallic complexes. This chapter deals with the challenges of the research in ab initio quantum chemistry particularly in its contribution to the modeling of organometallic systems with their inherent complexity. Including the contribution of NCIs into the analysis of chemical bonds and other bonding relationships is at reach with recently developed methods. Views and analyses of novel methodologies developed to produce a more accurate evaluation of the thermochemistry of reactions involving transition metal complexes in solution are presented. The intramolecular stabilizing role of NCIs is also reviewed for particular cases of bi...metallic d-block transition metal complexes that challenge, by their structural features, the empirical Langmuir-Sidgwick 18 electron rule. The treatment of the literature corpus of data is presented in a chronological fashion to outline the changes of practice over the years in the treatment of metal-metal interactions from a deductionist approach based on structural informations produced by static crystal X-ray diffraction analyses toward a comprehensive apprehension of bonding taking into consideration inherent molecular dynamics. Further review of intermolecular stabilizing effects of NCIs in peculiar cases of transition metal-based donor-acceptor complexes and other aggregates of transition metal complexes that display remarkable persistence in solution is presented. © 2016 John Wiley & Sons, Inc.
Keywords:Density functional theory / Intermolecular / Intramolecular / Non-covalent interactions / Transition metal
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