Coordination Behavior of ω-(Trichlorostannyl)alkyl Acetates, CH₃COO(CH₂)_nSnCl₃ (n = 3−5):  A Solution and Solid-State Multinuclear NMR and AM1 Quantum-Chemical Study

Abstract

The coordination behavior of three ester-functionalized monoorganotin trichlorides of the type ω-(trichlorostannyl)alkyl acetate, CH3COO(CH2) n SnCl3 (n = 3−5), has been investigated by multinuclear solid- and solution-state NMR, as well as AM1 quantum-chemical calculations. The data reveal basically the existence of a fast equilibrium between two species involved respectively in an intramolecular and intermolecular donor-acceptor interaction between the ester function and the tin atom. In the n = 3 case, the species involving the intramolecular interaction is by far the dominant one, with a coordination from the alkoxy oxygen atom to the tin atom, resulting in an interaction of the type −CH2O(Ac)→SnCl3 (Ac = CH3CO−). In contrast, for the n = 4 and 5 cases, the species involving the intermolecular interaction prevails, resulting in (cyclo)dimeric or oligomeric species displaying coordinations from the carbonyl oxygen atom to the tin atom of the type −CH2OC(CH3)O→SnCl3.

Structural study of C,N‐chelated monoorganotin(IV) halides

“…In order to explore the possibility of further complexation of fluoride ion, an excess of NH 4 F in methanol was added to 4e in an NMR tube. Based on 1 H, 19 F and 119 Sn NMR spectra parameters, the major species in solution was identified as 4a. The rest of the very minor signals in NMR spectra belong to the same complexes as depicted in Fig.…”

“…To a solution of 2 (200 mg, 0.4 mmol) in dichloromethane three molar equivalents of in high vacuo-dried NH 4 F were added and the reaction mixture was stirred for 5 days, then the solvent was removed in vacuo. A remaining crude solid was dissolved in methanol-d 4 19 F) = 2520 and 1169 Hz. To a toluene solution of 2 (100 mg, 0.2 mmol) was added 5 (235 mg, 0.61 mmol) and the reaction mixture was stirred and heated at 80…”

“…13 -23 To the best of our knowledge, there is only one paper dealing with synthesis and seven-coordinated and described by the authors as a distorted monocapped-trigonal-antiprism with Sn-F bond lengths from 1.948(7) to 1.975(6)Å and 1 J( 119 Sn, 19 F) being 3390 Hz in chloroform solution. A limited number of structurally related zwitterionic organostannates has been reported.…”

Catalytic properties of cross‐linked polystyrene grafted diorganotins in a model transesterification and the ring‐opening polymerization of ε‐caprolactone

“…26,36 The solid-state MAS spectra of compound 2 were recorded on the Bruker DRX250 spectrometer, operating at 89.25 MHz for the 117 Sn nucleus using procedures described previously. 45,46 Samples used for the determination of the ratio initial alcohol/obtained ester by solution 1 H NMR were prepared by dissolving about 10 mg of mixture in CDCl 3 (0.5 ml). In the case-study of the transesterification reaction of n-octanol with ethyl acetate, the quantitative liquid 1 H NMR spectra were recorded on a Bruker DRX250 Avance I spectrometer operating at 250.13 MHz.…”

Tributyl- and Triphenyltin Benzoates, Phenylacetates, and Cinnamates as Anion Carriers: an Electrochemical Assessment Coupled to Structural NMR Studies and AM1 Calculations

“…In view of both the relatively large size of the structures and the presence of an Sn-atom, a semi-empirical method was chosen for the energy and charge-distribution calculations. The AM1 method [41], for which the parameters for Sn have only recently been published [42], was selected, for its efficient applicability to a very wide range of chemical problems [43] and its successful application in structure-reactivity studies of tin compounds [44] [45].…”