“…The bond orders (BO) of the Sn−E bonds as defined in eq 4 have been used as a measure of the strength of such interactions. ,, Non-zero values can be related to the strength of the E−S interaction.…”
Section: Resultsmentioning
confidence: 99%
“…Compounds in which tin has the capacity to intramolecularly interact with sulfur or oxygen are well-studied, and several reviews of the subject can be found. , There are two major groups of organotins with such E−Sn intramolecular interactions: (A) the 1,1-dithiolates or η 2 -(O,O‘)-carboxylates, Figure a, , and (B) systems that bring oxygen or sulfur close to tin via “arms” of various carbon length as studied by Dräger 11-13 and others, , Figure b,c. The oxygen at the end of the carbon chain can be an ether or a carboxyl moiety, , whereas the majority of the sulfur systems involve simple aryl or alkyl sulfides. ,− 2 (a) General structure for 1,1-dithiolates and η 2 -( O , O ‘)-carboxylates. E = O, S; Y = NR 2 , OR, aryl/alkyl (b) Stannocanes which bring O or S in close proximity to Sn by 1,5 transannular interaction.…”
Section: Introductionmentioning
confidence: 99%
“…The oxygen at the end of the carbon chain can be an ether or a carboxyl moiety, 16,17 whereas the majority of the sulfur systems involve simple aryl or alkyl sulfides. 7,[18][19][20] Although our main focus is on tin chalcogen interactions, it is interesting to note that an analogous compound with an amino group in the ortho position has been reported. 21 The only crystal structure reported, however, is MePh[2-Me 2 -NC 6 H 4 CH(SiMe 3 )]SnBr in which the N-Sn distance is 2.492(3) Å (63% of the sum of the van der Waals radii for Sn and N).…”
Organotin(IV) compounds of the type (o-MeE-C6H4)CH2SnPh3-nCln were synthesized, E = O, n = 0 (1), n = 1 (2), n = 2 (3) and E = S, n = 0 (4), n = 1 (5), n = 2 (6). The complexes exhibit significant trigonal bipyramidal pentacoordination at tin as a consequence of intramolecular Sn-O (1-3) and Sn-S (4-6) interactions upon substitution of the phenyl groups by chloro groups. The intramolecular Sn-O distances in 1, 2, and 3 are 83%, 75%, and 79% of the sum of the van der Waals radii. The equivalent Sn-S values for 4, 5, and 6 are 90%, 73%, and 71%, respectively. The geometry of compound 3 is complicated by intermolecular dimerization via bridging chlorines creating a distorted octahedral geometry at tin. The related dichloro sulfur compound 6 also exhibits an intermolecular association in the form of Sn-Cl-H hydrogen bonding leading to a polymeric structure in the solid state. CPMAS 119Sn NMR spectroscopy suggests that the intramolecular Sn-E interactions persist in solution and also facilitated the discovery of a new crystalline form of 4, 4', that contains a Sn-S distance which is 95% the sum of the van der Waals radii.
“…The bond orders (BO) of the Sn−E bonds as defined in eq 4 have been used as a measure of the strength of such interactions. ,, Non-zero values can be related to the strength of the E−S interaction.…”
Section: Resultsmentioning
confidence: 99%
“…Compounds in which tin has the capacity to intramolecularly interact with sulfur or oxygen are well-studied, and several reviews of the subject can be found. , There are two major groups of organotins with such E−Sn intramolecular interactions: (A) the 1,1-dithiolates or η 2 -(O,O‘)-carboxylates, Figure a, , and (B) systems that bring oxygen or sulfur close to tin via “arms” of various carbon length as studied by Dräger 11-13 and others, , Figure b,c. The oxygen at the end of the carbon chain can be an ether or a carboxyl moiety, , whereas the majority of the sulfur systems involve simple aryl or alkyl sulfides. ,− 2 (a) General structure for 1,1-dithiolates and η 2 -( O , O ‘)-carboxylates. E = O, S; Y = NR 2 , OR, aryl/alkyl (b) Stannocanes which bring O or S in close proximity to Sn by 1,5 transannular interaction.…”
Section: Introductionmentioning
confidence: 99%
“…The oxygen at the end of the carbon chain can be an ether or a carboxyl moiety, 16,17 whereas the majority of the sulfur systems involve simple aryl or alkyl sulfides. 7,[18][19][20] Although our main focus is on tin chalcogen interactions, it is interesting to note that an analogous compound with an amino group in the ortho position has been reported. 21 The only crystal structure reported, however, is MePh[2-Me 2 -NC 6 H 4 CH(SiMe 3 )]SnBr in which the N-Sn distance is 2.492(3) Å (63% of the sum of the van der Waals radii for Sn and N).…”
Organotin(IV) compounds of the type (o-MeE-C6H4)CH2SnPh3-nCln were synthesized, E = O, n = 0 (1), n = 1 (2), n = 2 (3) and E = S, n = 0 (4), n = 1 (5), n = 2 (6). The complexes exhibit significant trigonal bipyramidal pentacoordination at tin as a consequence of intramolecular Sn-O (1-3) and Sn-S (4-6) interactions upon substitution of the phenyl groups by chloro groups. The intramolecular Sn-O distances in 1, 2, and 3 are 83%, 75%, and 79% of the sum of the van der Waals radii. The equivalent Sn-S values for 4, 5, and 6 are 90%, 73%, and 71%, respectively. The geometry of compound 3 is complicated by intermolecular dimerization via bridging chlorines creating a distorted octahedral geometry at tin. The related dichloro sulfur compound 6 also exhibits an intermolecular association in the form of Sn-Cl-H hydrogen bonding leading to a polymeric structure in the solid state. CPMAS 119Sn NMR spectroscopy suggests that the intramolecular Sn-E interactions persist in solution and also facilitated the discovery of a new crystalline form of 4, 4', that contains a Sn-S distance which is 95% the sum of the van der Waals radii.
Tetraorganotin compounds [2-(MeOCH2)C6H4]SnR3 (R = Me, n-Bu, Ph) containing a C,O-chelating ligand were prepared in good yield from the reaction of the R3SnCl and [2-(MeOCH2)C6H4]Li. Tethered organotin compounds Ph3Sn(CH2)3OC6H4R (R = Ph, H, CF3, OCH3) were prepared in good yield from the hydrostannylation reactions of the corresponding vinyl ethers with Ph3SnH. Conversion of two organotin compounds to triorganotin chlorides and diorganotin chlorides, (Ph3-nClnSn(CH2)3OC6H4R; R = H, Ph: n = 1, 2), was successfully carried out and characterisation afforded by NMR spectroscopy. X-ray crystallographic studies revealed a tetrahedral geometry for the tetraorganotin Ph3Sn(CH2)3OC6H4CF3, while five-coordinate trigonal bipyramidal structures with relatively short Sn-O (2.7-2.8 Å) interactions were observed for both mono- (Ph2ClSn(CH2)3OC6H4R; R = H, Ph) and dichloride (PhCl2Sn(CH2)3OC6H4R; R = H, Ph) species. Penta-coordinate diorganotin dichlorides containing a C,N- chelating ligand[2-(Me2NCH2)C6H4]RSnCl2 (R = Me, n-Bu, Ph) or C,O- chelating ligand [2-(MeOCH2)C6H4]RSnCl2 (R = Me, n-Bu, Ph) were prepared by treating RSnCl3 with the lithiated salts [2-(Me2NCH2)C6H4]Li and [2-(MeOCH2)C6H4]Li respectively. Organotin chlorides were successfully reduced with LiAlH4 or NaBH4 to produce novel hydrides. Catalytic dehydrocoupling of diorganotin dihydrides to yield polystannanes was explored using a variety of dehydrocoupling catalysts such as Wilkinson’s catalyst, Cp2ZrMe2 or TMEDA. In almost every instance this resulted in the formation of yellow coloured gummy polymeric materials of moderate molecular weights (Mw = 1 × 104 - 1 × 105 Da) and PDI’s (1.3-2.0). The stability of polystannanes containing
tethered O or C,N- or C,O-chelating ligands was investigated in both solid and in solution using NMR and UV-Vis spectroscopies. These studies revealed an enhanced stability to ambient light in the solid state and in solution in the dark when compared to known poly(dialkyl)stannanes.
Tetraorganotin compounds [2-(MeOCH2)C6H4]SnR3 (R = Me, n-Bu, Ph) containing a C,O-chelating ligand were prepared in good yield from the reaction of the R3SnCl and [2-(MeOCH2)C6H4]Li. Tethered organotin compounds Ph3Sn(CH2)3OC6H4R (R = Ph, H, CF3, OCH3) were prepared in good yield from the hydrostannylation reactions of the corresponding vinyl ethers with Ph3SnH. Conversion of two organotin compounds to triorganotin chlorides and diorganotin chlorides, (Ph3-nClnSn(CH2)3OC6H4R; R = H, Ph: n = 1, 2), was successfully carried out and characterisation afforded by NMR spectroscopy. X-ray crystallographic studies revealed a tetrahedral geometry for the tetraorganotin Ph3Sn(CH2)3OC6H4CF3, while five-coordinate trigonal bipyramidal structures with relatively short Sn-O (2.7-2.8 Å) interactions were observed for both mono- (Ph2ClSn(CH2)3OC6H4R; R = H, Ph) and dichloride (PhCl2Sn(CH2)3OC6H4R; R = H, Ph) species. Penta-coordinate diorganotin dichlorides containing a C,N- chelating ligand[2-(Me2NCH2)C6H4]RSnCl2 (R = Me, n-Bu, Ph) or C,O- chelating ligand [2-(MeOCH2)C6H4]RSnCl2 (R = Me, n-Bu, Ph) were prepared by treating RSnCl3 with the lithiated salts [2-(Me2NCH2)C6H4]Li and [2-(MeOCH2)C6H4]Li respectively. Organotin chlorides were successfully reduced with LiAlH4 or NaBH4 to produce novel hydrides. Catalytic dehydrocoupling of diorganotin dihydrides to yield polystannanes was explored using a variety of dehydrocoupling catalysts such as Wilkinson’s catalyst, Cp2ZrMe2 or TMEDA. In almost every instance this resulted in the formation of yellow coloured gummy polymeric materials of moderate molecular weights (Mw = 1 × 104 - 1 × 105 Da) and PDI’s (1.3-2.0). The stability of polystannanes containing
tethered O or C,N- or C,O-chelating ligands was investigated in both solid and in solution using NMR and UV-Vis spectroscopies. These studies revealed an enhanced stability to ambient light in the solid state and in solution in the dark when compared to known poly(dialkyl)stannanes.
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