Synthesis, characterization and selective de-esterification of diorganotinbis(O-methylphosphite)s

Shankar, Ravi; Asija, Meenal; Singla, Nisha; Basu, Suddhasatwa; Kociok‐Köhn, Gabriele; Molloy, Kieran C.

doi:10.1039/c3dt52178h

Cited by 4 publications

(4 citation statements)

References 57 publications

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“…15 The structural similarities between the two families are quite apparent in view of the formation of one-dimensional coordination polymers that result from the bridging bidentate bonding mode of phosphonate/phosphite ester ligands. Due to their low-dimensional structural frameworks, both classes of compounds show enhanced solubility in water/organic solvents.…”

Section: Spectral Studiesmentioning

confidence: 98%

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

et al. 2014

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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.

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Section: Spectral Studiesmentioning

confidence: 98%

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

et al. 2014

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“…20 Our contribution in this area r e l a t e s t o t h e s y n t h e s i s o f d i o r g a n o t i n b i s (Oalkylorganophosphonate)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. 21,22 The reaction proceeds via the selective cleavage of the (P)O−C bond and the elimination of alkyl halide as the byproduct.…”

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confidence: 66%

“…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.…”

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confidence: 99%

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

et al. 2017

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A new recipe for the synthesis of diorganotin bis(O-alkylorganophosphonate)s, RSn{O(P)(O)(OR)R} [R = R = methyl (1); R = ethyl and R = methyl (2), allyl (3), 2-thienyl (4), benzyl (5)], has been developed from the direct reaction of elemental tin (powder) with organophosphonic acid dialkyl esters, RP(O)(OR), in the presence of a catalytic amount of potassium iodide under ambient conditions (130 °C, 18-20 h). The key steps in the proposed catalytic cycle involve the monodealkylation of phosphonate diester and in situ generation of a RSnI or RSnI intermediate via the oxidative addition of alkyl iodide on tin. Evidence in support of the formation of organotin species comes from the isolation of MeSn{O(P)(O)(OPr)Me} (6) from the direct reaction of tin metal with MeP(O)(OPr) in the presence of methyl iodide. The method has also been extended to isolate Zn{OP(O)(OMe)Me} (7) using metallic zinc as the precursor. All of the compounds have been characterized by IR and NMR studies as well as X-ray crystallography for 2, 4, 6, and 7.

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“…It is important to emphasize that coordination chemistry of these ligands still remains in a state of dormancy despite a few early reports on the synthesis of sila-substituted phosphonic acids . As part of our ongoing interest in metal coordination frameworks derived from oxyphosphorus-based ligands, , we surmised that incorporation of these ligands in the coordination assemblies might offer a possibility to modulate structural motifs as a result of steric and electronic attributes of silaalkyl groups. Herein we report a detailed study on the synthesis and structural aspects of two new silaalkylphosphonic acids, namely, Me 3 SiCR 2 P(O)(OH) 2 [R = H ( 1 ), CH 3 ( 2 )] and diorganotin(IV) coordination polymers Et 2 Sn{OP(O)(OH)CH 2 SiMe 3 }(OSO 2 Me) ( 3 ), (Et 2 Sn) 6 {O 3 PC(CH 3 ) 2 SiMe 3 } 4 (OSO 2 Me) 4 ( 4 ), and Et 2 Sn(O 3 PCH 2 SiMe 3 ) ( 5 ) derived therefrom.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Studies of Diorganotin(IV)-Based Coordination Polymers Bearing Silaalkylphosphonate Ligands and Their Transformation into Colloidal Domains

et al. 2014

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The contribution of silaalkylphosphonic acids Me3SiCH2P(O)(OH)2 (1) and Me3SiC(CH3)2P(O)(OH)2 (2) as ligands was demonstrated for the first time by the isolation of new diorganotin(IV) phosphonates Et2Sn{OP(O)(OH)CH2SiMe3}(OSO2Me) (3), (Et2Sn)6{O3PC(CH3)2SiMe3}4(OSO2Me)4 (4), and Et2Sn(O3PCH2SiMe3) (5). X-ray crystallographic studies of 1-4 are presented. The structures of 1 and 2 adopt extended motifs by virtue of P-OH···O═P-type hydrogen bonding interactions. The molecular structure of 3 is composed of a dimer formed by bridging hydrogen phosphonate groups, while the sulfonate group appended on each tin atom acts in a μ2-bridging mode to afford the formation of one-dimensional coordination polymer featuring alternate eight-membered [-Sn-O-P-O-]2 and [-Sn-O-S-O-]2 rings. The asymmetric unit of 4 is composed of two crystallographically unique trinuclear tin phosphonate clusters with a Sn3(μ3-PO3)2 core linked together by coordinative association of a μ2-sulfonate group, while the remaining sulfonates are involved in the construction of a two-dimensional self-assembly. The identity of 1-5 in solution was established by IR and multinuclear ((1)H, (13)C, (31)P, (119)Sn) NMR spectroscopy. The presence of silaalkyl group in 5 imparts unusual solubility in hydrocarbon, aromatic, and ether solvents. As a consequence, the formation of colloidal particles of 5 featuring rodlike morphology was achieved by ultrasonication of a solution in ethanol-chloroform mixture.

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Synthesis, characterization and selective de-esterification of diorganotinbis(O-methylphosphite)s

Cited by 4 publications

References 57 publications

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

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

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

Synthesis and Structural Studies of Diorganotin(IV)-Based Coordination Polymers Bearing Silaalkylphosphonate Ligands and Their Transformation into Colloidal Domains

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