Abstract
AbstractA nitrosyl ligand is bonded to a central metal mainly via a mostly covalent normal bond and a coordinative metal‐to‐NO π‐backbond. A recent analysis had unravelled similar bonding characteristics of both linear and bent CoNO moieties in terms of ligand charge and antibond occupation. Thus, there should be no justification for the usual assignment of an NO+ ligand to a linear MNO unit and a singlet‐NO− ligand to a bent one. This claim seems to contradict that bending an MNO unit weakens the N−O bond with a marked red‐shift of the N−O stretch as one indicator. In this work, the failure of Dewar‐Chatt‐Duncanson‐derived conclusions is demonstrated for linear/bent isomer couples by the analysis of M−N and N−O bond strengths. Instead of DCD behavior, lateral electrostatic influence on NO and other diatomic ligands modulates the intraligand bond strength in a similar way as has been shown in former work for polar interaction of a charge with CO in the ‘non‐classical’ carbonyls. Methodologically, local‐mode analysis is used to determine bond strengths. Oxidation states are determined by the effective‐oxidation‐state (EOS) method.
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