Synthesis, characterization and hydrolytic stability of diorganotin(IV)bis(O-alkyl alkylphosphonate)s

Abstract

Diorganotinbis(O-alkyl alkylphosphonate)s, R 2 Sn(O 2 P(OR 1 )R 1 ) 2 [R 1 = Me, R = Me (1), Et (2), n-Bu (3); R 1 = Et, R = Me (4), Et (5), n-Bu (6)] have been synthesized from the reaction between dimethyl/diethyl/di-n-butyltin dichloride and dialkyl alkylphosphonates, (R 1 O) 2 P(O)R 1 , in a solvent-free medium (120°C, 18 h). X-ray crystal structure of 1 reveals two independent molecules in the unit cell that form one-dimensional polymeric motifs by virtue of bridging bidentate phosphonate groups. The structural attribute of each polymeric chain represents an orderly infinite array of -[Sn-O-P-O-] 2 8-membered puckered cyclic rings with hexa-coordinated tin atoms. The structure of 2 resembles that of 1 and exhibits nearly identical structural parameters. The presence of C-H···O hydrogen bonding interactions involving P-OMe and (or) phosphonate (P=O) groups in both 1 and 2 afford the formation of two-and three-dimensional structural motifs, respectively. The phase purity and structural integrity of the bulk sample of 1 upon exposure to water has been ascertained by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). All the compounds reported herein have been characterized by IR and multinuclear ( 1 H, 13 C, 31 P, 119 Sn) NMR spectral studies.Résumé : Des diorganoétains bis(O-alkyl alkylphosphonate), de formule R 2 Sn(O 2 P(OR 1 )R 1 ) 2 [R 1 = Me, R = Me (1), Et (2), n-Bu (3); R 1 = Et, R = Me (4), Et (5), n-Bu (6)] ont été synthétisés à partir de la réaction entre dichlorure de diméthyl (ou diéthyl-ou di-n-butyl-) étain et des dialkyl alkylphosphonates, de formule (R 1 O) 2 P(O)R 1 , dans un milieu sans solvant (à 120°C, pendant 18 h). La structure de 1, déterminée par cristallographie aux rayons X, montre deux molécules indépendantes dans la cellule unitaire qui forme des motifs polymériques unidimensionnels au moyen de groupes bidentate phosphonate pontants. La structure de chacune des chaînes polymériques se caractérise par une série ordonnée et infinie d'anneaux cycliques plissés à huit membres, -[Sn-O-P-O-] 2 , associés des atomes d'étain hexacoordonnés. La structure de 2 ressemble à celle de 1 et tous deux possèdent des paramètres structuraux presque identiques. La présence d'interactions par liaison hydrogène C-H···O, auxquelles participent des groupes P-OMe et (ou) phosphonate (P=O), dans les composés 1 et 2 permet la formation de motifs structuraux respectivement bidimensionnel et tridimensionnel. La pureté de phase et l'intégrité structurale de l'échantillon brut de 1 lorsqu'il est exposé à l'eau ont été vérifiées par diffractométrie de rayons X sur poudre (XRD) et microscopie électronique à balayage (SEM). Tous les composés identifiés dans la présente étude ont été caractérisés par des analyses spectroscopiques infrarouges et RMN multinucléaires ( 1 H, 13 C, 31 P, 119 Sn). [Traduit par la Rédaction] Mots-clés : ester phosphonate, organoétain, hydrolyse, chimie de coordination.

Reactivity of Elemental Tin and Zinc toward Organophosphonic Acid Dialkyl Esters: A New One-Pot Recipe for the Synthesis of Coordination Assemblies Derived from O-Alkylorganophosphonate Ligands

“…Zuckerman et al have reported the synthesis of cyclohexameric triphenyltin O -methylmethylphosphonate, [Ph 3 SnOP­(O)­(OCH 3 )­CH 3 ] 6 , by a series of complex steps involving the Arbuzov rearrangement of a Ph 3 SnOP­(OCH 3 ) 2 intermediate . Our contribution in this area relates to the synthesis of diorganotin bis­( O -alkylorganophosphonate)­s, R 2 Sn­{O­(P)­(O)­(OR)­R} 2 , and their H -phosphonate analogues from the direct reaction between diorganotin dichloride and the corresponding organophosphonic acid dialkyl ester/ H -phosphonic acid dialkyl ester. , The reaction proceeds via the selective cleavage of the (P)­O–C bond and the elimination of alkyl halide as the byproduct.…”

“…The result finds an analogy with an earlier report on the oxidative addition of phosphate esters on metallic zinc . The IR and NMR spectroscopic data of 1 (see the Supporting Information, SI) are identical with those of an authentic sample obtained from the reaction of dimethyltin dichloride with methylphosphonic acid dimethyl ester …”

Growth modulation of bent micro crystals to single crystals in a one-dimensional coordination framework

“…11 In continuation of our recent studies on the synthesis and structural aspects of diorganotin(IV) phosphonate esters, R 2 Sn {OP(O)(OMe)Me} 2 (R ¼ Me, Et), we have drawn our attention to a unique crystal growth behaviour of n-Bu 2 Sn{OP(O)(OMe)Me} 2 (1) which has been previously characterized by spectroscopic methods. 12 Upon evaporation induced crystallization of 1 from a solution in chloroform, bre-like crystallites of several microns in length were obtained. The phenomenon has also been observed in chloroform-acetonitrile and chloroformether solvent mixtures.…”

“…The tin atoms in the polymeric chains adopt a distorted octahedral geometry with equatorial SnO 4 core [ P 360 AE 0 ] and trans n-butyl groups [:C-Sn-C ¼ 180.0(0) ] while other metrical parameters resemble closely with those reported earlier for analogous dialkyltinbis(O-methylmethylphosphonate)s. 12 The inorganic chains comprising of [-Sn-O-P-O-] 2 rings run along crystallographic a-axis while the presence of weak C-H/O hydrogen bonds is discernable along the crystallographic c-axis. The orientation of secondary interactions approximately orthogonal to the linear inorganic chains provides anisotropy in the crystals and nds a close analogy with several reported examples of organic molecules exhibiting bent phenomenon.…”

Preface for the Special Issue dedicated to the 14th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL 2013)

“…The purpose of this conference was to bring together researchers whose interests span the chemistry of germanium, tin, and lead, and this collection of manuscripts reflects the diverse range of topics presented at the conference: from the synthesis of low coordinate molecules as illustrated in the work presented by Jones 1 and studies of the reactivity of these interesting species as reported by Růžička, 2 Tokitoh 3 Willem, 4 and Baines 5 to the synthesis of high coordinate supramolecular structures as demonstrated in the work of Reuter; 6,7,8 from muon spin spectroscopy of germanium radicals as studied by West 9 to nuclear magnetic resonance spectroscopy 4 of Sn(II) and Sn(0) complexes; from the synthesis of ternary metal clusters as reported by Molloy 10 to polymers and their model oligomers as synthesized by Foucher 11 and Weinert, 12 respectively. Saito, 13 Shankar, 14 and Uhlig 15,16 describe their research on the high yielding synthesis and extended structures of several important functional tin(IV) compounds. Finally, the elegant synthesis of a mixed Group 14 propellane was reported by Breher.…”