0000000000088514
AUTHOR
Romain Burgat
Reactivity of di-tert-butyldimethoxystannane with carbon dioxide and methanol: X-ray structure of the resulting complex
Abstract The synthesis of dimethyl carbonate from carbon dioxide and methanol was studied with ditert-butyldimethoxystannane under pressure at temperatures ⩽423 K. The formation of dimethyl carbonate is accompanied by transformation of the stannane into a trinuclear complex, the structure of which has been determined by single-crystal X-ray diffraction technique. The relevance of this specie in the catalytic cycle is demonstrated by conducting recycling runs. A preliminary kinetic study underlines the steric influence of the tert-butyl ancillary ligands in the stabilisation of intermediates, by comparison with the n-butyl homologue.
New Insights into the complexation of lead(II) by 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (DOTAM): structural, thermodynamic and kinetic studies
The lead(II) coordination properties of the tetrapodal ligand DOTAM [1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraaza-cyclododecane] have been investigated both in the solid state and in solution in order to ascertain the stereoactivity of the lone pair and to rationalize the structural effects of a cyclen-based scaffold on the metal uptake kinetics. The crystal structure of the free base shows that the pendant acetamide groups are not equivalent: two are folded over the macrocycle and maintained by an intramolecular hydrogen bond involving an amide hydrogen atom and a neighboring tertiary amine of the cyclen ring, while the other two are extended and point away from the macrocyclic cav…
Thermodynamic studies of actinide complexes. 1. A reappraisal of the solution equilibria between plutonium(IV) and ethylenediaminetetraacetic acid (EDTAH4) in nitric media
Abstract A detailed reevaluation of the complexation equilibria of plutonium(IV) with the polyaminocarboxylic sequestering agent EDTA4− has been performed in 1 M (H,K)NO3 media at 298 K by means of visible absorption spectrophotometry and glass-electrode potentiometry at millimolar concentration levels. The high binding affinity even under strongly acidic conditions supports the exclusive formation of the neutral Pu(EDTA) complex over the range 0.01 ≤ [H+] ≤ 0.9 M with an apparent formation constant of log β110 = 25.8(1) at 0.9 M HNO3. Extrapolation to zero ionic strength using the SIT approach provides the first ever-reported NEA–TDB compliant estimate of β 110 0 ( log β 110 0 = 32.2 ( 3 )…
The ionic tin(IV) complex tri-μ2-methoxy-μ3-oxo-tris[di-tert-butyltin(IV)] tri-μ2-methoxy-bis[tert-butyldimethoxystannate(IV)]
The solid-state of the title compound, [Sn3(C4H9)6(CH3O)3O][Sn2(C4H9)2(CH3O)7], consists of distinct [tBu6Sn3(μ-OCH3)3(μ3-O)]+ cations and [tBu2Sn2(OCH3)4(μ-OCH3)3]− anions, apparently formed as a result of slow hydrolysis of pure di(tert-butyl)dimethoxystannane, tBu2Sn(OCH3)2. In the monocation, the coordination about the Sn atoms is distorted trigonal bipyramidal, and, in the monoanion, distorted octahedral. The trigonal bipyramidal arrangement induces planarity of the Sn3O4 motif.