A DFT study of the vicinal 3J(119Sn,13C) and 3J(119Sn,1H) coupling constants in trimethyl- and chlorodimethylstannyl propanoates

We have tested the performance of DFT protocols, both at the Scalar relativistic ZORA and non-relativistic level of theory, for the calculation of the 3J(119Sn,13C) and 3J(119Sn,1H) vicinal couplings for a series of flexible organotin(IV) derivatives with formula XMe2SnCHRCHR′COOMe (X = Me, Cl; R, R′ = Me, Ph). A satisfactory agreement between experimental and calculated vicinal couplings has been obtained by taking into account the conformational behaviour of the compounds investigated. The protocols used, mainly the relativistic one, were found to give a correct picture of the populations and a sufficiently high overall performance in calculating the vicinal couplings, thereby overcoming the use of empirical Karplus-type relationships to infer geometrical parameters from 3J(119Sn,13C) and 3J(119Sn,1H).

ZORA relativistic and non-relativistic DFT methods showed to satisfactorily reproduce both conformational population and 3J(119Sn–C–C–1H), 3J(119Sn–C–C–13C) values for a series of flexible organotin(IV) derivatives. The proposed protocols allow to overcome the use of empirical Karplus-type relationships for the structural analysis for this class, and analogous ones, of organotin(IV) derivatives.Figure optionsDownload as PowerPoint slideHighlights
► DFT protocols allow to well reproduce 3J(119Sn,13C) and 3J(119Sn,1H) vicinal couplings for a series of flexible organotin(IV) derivatives.
► A reliable picture of the conformers populations is obtained both a relativistic and non-relativistic level of theory.
► Computational approach overcomes the necessity to parameterize ad hoc Karplus-type equations for organotin(IV) derivatives.