- [n-Bu2NH2]3[SnPh3(SeO4)2]: The first triorganotin(IV) complex with terminally coordinated selenato ligands
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The reaction of SeO4 H2 and SnPh3 OH in the presence of n-Bu2 NH led to the formation of [(n-Bu2 NH2)]3[SnPh3(SeO4)2] (1), which crystallizes in the orthorhombic space group P21 21 21 with Z=4, a=16.2509(7) ?, b=17.2412(8) ?, c=17.6881(5) ?, and V=4955.9(3) ?3. The structure of the novel trianion of 1 consists of a SnPh3 moiety trans-coordinated by two monodentate selenato ligands involving a trigonal bipyramid geometry around the Sn(IV) atom. The charges of [SnPh3(SeO4)2]3- are compensated by three [n-Bu2 NH2]+ cations. From a supramolecular point of view, the three uncoordinated oxygen atoms of each selenato ligand are involved in hydrogen bonding interactions with the surrounding di-n-butylammonium cations through N-H···O contacts, leading to a three-dimensional network. The structural characterization of salt 1 was completed by infrared and NMR spectroscopy and elemental analysis, which confirm the X-ray elucidation.
- Diallo, Waly,Diop, Libasse,Plasseraud, Laurent,Cattey, Hlne
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- Mechanistic Pathways for N2O Elimination from trans-R3Sn-O-N=N-O-SnR3and for Reversible Binding of CO2to R3Sn-O-SnR3(R = Ph, Cy)
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The rate and mechanism of the elimination of N2O from trans-R3Sn-O-N=N-O-SnR3 (R = Ph (1Ph) and R = Cy (1Cy)) to form R3Sn-O-SnR3 (R = Ph (2Ph) and R = Cy (2Cy)) have been studied using both NMR and IR techniques to monitor the reactions in the temperature range of 39-79 °C in C6D6. Activation parameters for this reaction are ΔH? = 15.8 ± 2.0 kcal·mol-1 and ΔS? = -28.5 ± 5 cal·mol-1·K-1 for 1Ph and ΔH? = 22.7 ± 2.5 kcal·mol-1 and ΔS? = -12.4 ± 6 cal·mol-1·K-1 for 1Cy. Addition of O2, CO2, N2O, or PPh3 to sealed tube NMR experiments did not alter in a detectable way the rate or product distribution of the reactions. Computational DFT studies of elimination of hyponitrite from trans-Me3Sn-O-N=N-O-SnMe3 (1Me) yield a mechanism involving initial migration of the R3Sn group from O to N passing through a marginally stable intermediate product and subsequent N2O elimination. Reactions of 1Ph with protic acids HX are rapid and lead to formation of R3SnX and trans-H2N2O2. Reaction of 1Ph with the metal radical ?Cr(CO)3C5Me5 at low concentrations results in rapid evolution of N2O. At higher ?Cr(CO)3C5Me5 concentrations, evolution of CO2 rather than N2O is observed. Addition of 1 atm or less CO2 to benzene or toluene solutions of 2Ph and 2Cy resulted in very rapid reaction to form the corresponding carbonates R3Sn-O-C(=O)-O-SnR3 (R = Ph (3Ph) and R = Cy (3Cy)) at room temperature. Evacuation results in fast loss of bound CO2 and regeneration of 2Ph and 2Cy. Variable temperature data for formation of 3Cy yield ΔHo = -8.7 ± 0.6 kcal·mol-1, ΔSo = -17.1 ± 2.0 cal·mol-1·K-1, and ΔGo298K = -3.6 ± 1.2 kcal·mol-1. DFT studies were performed and provide additional insight into the energetics and mechanisms for the reactions.
- Captain, Burjor,Davis, Jack V.,Gamage, Mohan M.,Guio, Oswaldo,Hoff, Carl D.,Temprado, Manuel
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supporting information
p. 12075 - 12084
(2021/08/24)
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- Synthesis and properties of Ph3Sn substituted tellurates - The crystal structures of trans-[(Ph3SnO)4Te(OH)2] and trans-[(Ph3SnO)2Te(OMe)4]
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The reaction of Te(OH)6 with Ph3SnOH in ethanol leads to the formation of trans-[(Ph3SnO)4Te(OH)2] (1). Compound 1 crystallizes triclinic in the space group P1 with a = 996.6(2) pm, b = 1365.4(3) pm, c = 1368.2(3) pm and α = 71.15(2)°, β = 71.48(2)°, γ = 74.81(3)° (at 220 K). The molecular structure of 1 consists of a tellurium atom, which is coordinated nearly octahedrally by four Ph3SnO units and two hydroxyl groups that are trans to each other. The Te-O bond lengths are in the range of 190.5(2) and 193.7(2) pm. Treatment of 1 with methanol under reflux yields trans-[(Ph3SnO) 2Te(OMe)4] (2). Compound 2 crystallizes triclinic in the space group P1 with a = 1012.8(1) pm, b = 1422.4(2) pm, c = 1618.1(2) pm, and α = 100.44(1)°, β = 107.92(1)°, γ = 110.66(1)° (at 220 K). 2 forms centrosymmetric molecules in which the tellurium atom is surrounded nearly octahedrally by four methoxy groups and two trans arranged Ph3SnO units. The Te-O bond lengths of 187.9(3)-194.5(3) pm are similar to those observed in 1.
- Heratrich, Tobias,Merzweiler, Kurt
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p. 803 - 807
(2010/09/04)
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- Structure, properties and cytostatic activity of triorganotin (aminoaryl)carboxylates
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The properties of vinyltin and phenyltin complexes [Sn(CH=CH2)3{μ-OOCC6H3 (NH2)2-3,4}]n (1), [Sn(C6H5)3- {OOCC6H3(NH2)2-3,4}] (2), [Sn(C6H5)3{OOC-2-C6H4 N= NC6H4N(CH3)2-4})] (3) and [Sn(CH=CH2)3{OOC-2-C6H4N= NC6H4N(CH3)2-4}] (4) have been investigated. The structures of complexes 1, 2, and 3, have been determined by X-ray crystallography, Compound 1 is a distorted trigonal-bipyramidal complex and compounds 2 and 3 adopt a distorted tetrahedral structure. Complex 1 is a single-strand polymer with a bridging 3,4-diaminobenzoato ligand coordinating via the O(1) atom of the carboxylato group and the nitrogen atom of the para-amino group. The oxygen and nitrogen atoms occupy the axial coordination sites. The Sn(1)-N(2A) bond is weak. In complexes 2 and 3 the carboxylato hgands are strongly coordinated to the central atom via one oxygen atom, and the Sn(1)-O(2) distances are considerably longer. Weak interactions of the central atom with the amino group in complex 1, and with the O(2) atoms in complexes 2 and 3, as well as the hydrogen bonds, stabilize the crystal structure. The complexes are effective cytostatic agents. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
- Pruchnik, Florian P.,Banbula, Malgorzata,Ciunik, Zbigniew,Chojnacki, Henryk,Latocha, Malgorzata,Skop, Barbara,Wilczok, Tadeusz,Opolski, Adam,Wietrzyk, Joanna,Nasulewicz, Anna
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p. 3214 - 3221
(2007/10/03)
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- Organotin Biocides. XIII. C-Triorganostannylimidazoles, -benzoxazoles and -benzothiazoles
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The synthesis, spectroscopic characterisation, and reactivity of a series of triorganotin imidazoles, benzothiazoles and benzoxazoles R3Sn(Het) (R=Me, Bu, Ph) are described.The structure of 2-(triphenylstannyl)benzothiazole has been determined by crystallographic methods.Space group: Triclinic, P1; a 9.501(1), b 10.172(2), c 13.231(2) Angstroem, β 70.46(1), γ 69.71(1) deg, U 1082.8 Angstroem3, F(000)=484, μ(Mo-Kα) 11.74 cm-1, R=0.0719 for 2264 reflections with I>3?I.The geometry at the tin is tetrahedral.Bond angles at tin are used to discuss the reactivity and Moessbauer spectra of these species.
- Molloy, Kieran C.,Waterfield, Philip C.,Mahon, Mary F.
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- Mixed triorganotin compounds, R3Sn-X-SnR'3: 119Sn NMR evidence for their formation in solution
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119Sn NMR spectroscopy has been used to demonstrate the existence, for hte first time, of mixed triorganotin compounds, R3Sn-X-SnR'3, where R or R' = Bu, Ph or cyclo-C6H11 and X = O or S.These species exist in solution in equilibrium with the correspondin
- Blunden, S. J.,Hill, R.
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p. 317 - 322
(2007/10/02)
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