Bis(μ²-2-(dimethylamino)ethoxo-N,O,O)-di(phenolato-O)ditin(II): a high-resolution single-crystal X-ray diffraction and quantum chemical study

Abstract

Experimental and calculated electron density functions ρ(r) of the title compound in the crystal were obtained. These were compared with ρ(r) for an isolated dimer. Application of the `Atoms in Molecules' theory allowed the visualization of the electron lone pair (Lp) of tin(II) and the calculation of some bond energies and all atomic charges. The stereochemical activity of the Lp was demonstrated and its volume was estimated to be approximately 10 Å(3). The energies of N→Sn and Sn-O bonds were found to be 13-18 and 25-52 kJ mol(-1). According to the experimental, AM05-PW and PBE0/6-311G(d,p) calculation data, µ(2)-2-(dimethylamino)ethoxoate accepts 0.68, 0.45 and 0.40 e from the Sn atom. Using the example of µ(2)-2-(dimethylamino)ethoxoates and complexes of bis(n-butyl)tin(IV) it was demonstrated that the more screened the Sn atom, the better the catalytic activity of its complex in polyurethane synthesis.

Understanding the structure of salicyl hydrazone metallocomplexes: crystal structure, AIM and Hirshfeld surface analysis of trichloro-(N-salicylidenebenzoylhydrazinato-N,O,O′)-tin(IV)

“…The energies of Sn-Cl bonds vary from 27 to 43 kcal/mol that are less than half of Sn-Cl energy in Me 3 SnCl (101.6 kcal/mol) [62]; similarly, the Sn-O bonds are also much weaker (24-67 kcal/mol) compared to single bond of this type (90.6 kcal/mol) [62]. E bond (Sn-O) in 1 is in the range obtained for Sn 2 (OCH 2 CH 2 NMe 2 ) 2 (OPh) 2 (24-52 kcal/mol) [20] and also in good accord with the ΔH value of hydroxydistannoxane dimerization (MP2/6-311 + G(d)) (49.7 kcal/mol) [63]. At the same time, value of E bond (Sn-N) = 24-45 kcal/mol in 1 significantly varies from those previously calculated (9, 15 and 13-18 kcal/mol for [(Me 3 Si) 2 NSnL] 2 [64], phthalocyaninatotin(II) [65] and Sn 2 (OCH 2 CH 2 NMe 2 ) 2 (OPh) 2 ) [20].…”

“…E bond (Sn-O) in 1 is in the range obtained for Sn 2 (OCH 2 CH 2 NMe 2 ) 2 (OPh) 2 (24-52 kcal/mol) [20] and also in good accord with the ΔH value of hydroxydistannoxane dimerization (MP2/6-311 + G(d)) (49.7 kcal/mol) [63]. At the same time, value of E bond (Sn-N) = 24-45 kcal/mol in 1 significantly varies from those previously calculated (9, 15 and 13-18 kcal/mol for [(Me 3 Si) 2 NSnL] 2 [64], phthalocyaninatotin(II) [65] and Sn 2 (OCH 2 CH 2 NMe 2 ) 2 (OPh) 2 ) [20].…”

“…[16,17] for instance) or analysis of HOMO and LUMO in tin complexes [18]. Besides, the chemical bonding in the donor-acceptor complexes of SnCl 4 and SnBr 4 was studied and the energies of some Sn-O and Sn-N bonds were estimated [19,20]. Apart from bonding description, the atomic characteristics and spatial features of the electron structure are also of interest.…”

“…Until now, the results of topological analysis of tincontaining compounds are limited to two hypothetical stannatranes [22], the complex [Sn(C 7 H 8 ) 3 ] 2+ dication [23], the low-coordinated tin Sn 2 (OCH 2 CH 2 NMe 2 )(OPh) dimer [20], hexacoordinated tin(IV) [24] and phenyl (triphenylstannyl)telluride [25,26]. According to the AIM theory, information on chemical bonding can be obtained analyzing the local minima, maxima, and saddle points of the electron density ρ(r) function.…”

Insight into the Electron Density Distribution in an O,N‐Heterocyclic Stannylene by High‐Resolution X‐ray Diffraction Analysis

“…Nevertheless, up to date there is not enough experimental information about the distribution of electron density in tin(II,IV) complexes . To the best of our knowledge, no detailed experimental studies concerning the nature and topological characteristics of Sn‐Sn bonds in distannenes have been published so far.…”