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

摘要

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(~(119)Sn,~(13)C) and ~3J(~(119)Sn,~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(~(119)Sn,~(13)C) and ~3J(~(119)Sn,~1H).