Mild formation of cyclic carbonates using Zn(II) complexes based on N2S2-chelating ligands

Anselmo, Daniele; Bocokić, Vladica; Decortes, Antonello; Escudero‐Adán, Eduardo C.; Benet‐Buchholz, Jordi; Reek, Joost N. H.; Kleij, Arjan W.

doi:10.1016/j.poly.2011.05.025

Cited by 27 publications

(9 citation statements)

References 29 publications

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“…In this arrangement, there is a C 2 axis located perpendicular to the Zn 2 S 2 rhomboid. This is in contrast to other related structures where a trans arrangement, due to a center of inversion in the middle of the rhomboid, was observed (Anselmo et al, 2012;Almaraz et al, 2008;Buncic et al, 2010;Cowley et al, 2002;Shaban, 2011;Tuntulani et al, 1992).…”

Section: Resultscontrasting

confidence: 99%

Bis{μ-2,2′-[(butane-2,3-diylidene)bis(azanylylidene)]dibenzenethiolato}dizinc(II)–dimethyl sulfoxide–methanol (2/0.18/0.82)

2013

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The asymmetric unit in the crystal structure of the title compound, [Zn2(C16H14N2S2)2]2·0.18C2H6OS·0.82CH3OH, consists of two ordered bis{μ-2,2'-[(butane-2,3-diylidene)bis(azanylylidene)]dibenzenethiolato}dizinc(II) molecules and a disordered solvent combination at the same location which refined to 18.1 (7)% dimethyl sulfoxide and 81.9 (7)% methanol. The compound has a metallic cluster structure formed by the joining together of two zinc(II) complex molecules, forming a rhomboidal Zn2S2 arrangement. This complex was previously suggested on the basis of nonstructural evidence to be a monomer [Jadamus, Fernando & Freiser (1964). J. Am. Chem. Soc. 86, 3056-3059]. Each Zn(II) atom is five-coordinated and exhibits distorted trigonal bipyramidal geometry. The structure may be of interest with respect to zinc-thiolate bonds, the coordination chemistry of Schiff bases and the folding of proteins. The structure displays weak intermolecular C-H···S, C-H···O and C-H···N interactions, and contains a unique bonding arrangement of the ligands around the Zn2S2 rhomboid.

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Section: Resultscontrasting

confidence: 99%

Bis{μ-2,2′-[(butane-2,3-diylidene)bis(azanylylidene)]dibenzenethiolato}dizinc(II)–dimethyl sulfoxide–methanol (2/0.18/0.82)

2013

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“…The association constants ( K 1.1 ) of A with meta ‐ and para ‐substituted 2 , 3 , 5 and 6 halopyridine derivatives determined by UV/Vis titrations using toluene as solvent were found to be 1.0×10 4 , 9.0×10 3 , 1.9×10 4 , and 1.9×10 4 m −1 , respectively (see the Supporting Information) . Although UV/Vis changes during titration were small, they were sufficient to produce well‐behaved titration curves, which were used to calculate the association constants K 1.1 (see the Supporting Information) ,. The binding constants K 1.1 determined for 2 ⋅ A and 5 ⋅ A are only slightly higher compared to previous reports in which the titrations were performed using a different solvent; that is, dichloromethane .…”

Section: Resultsmentioning

confidence: 77%

Palladium‐Catalysed Cross‐Coupling Reactions Controlled by Noncovalent Zn⋅⋅⋅N Interactions

Kadri

Hou

Dorcet

et al. 2017

Chemistry A European J

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Non-covalent interactions between halopyridine substrates and catalytically inert building blocks, namely zinc(II)-porphyrins and zinc(II)-salphens, influence the catalytic outcome of Suzuki-Miyaura and Mizoroki-Heck palladium-catalysed cross-coupling reactions. The weak Zn⋅⋅⋅N interactions between halopyridine substrates and zinc(II)-containing porphyrins and salphens, respectively, were studied by a combination of H NMR spectroscopy, UV/Vis studies, Job-Plot analysis and, in some cases, X-ray diffraction studies. Additionally, the former studies revealed unique supramolecular polymeric and dimeric rearrangements in the solid state featuring weak Br⋅⋅⋅N (halogen bonding), C-H⋅⋅⋅π, Br⋅⋅⋅π and π⋅⋅⋅π interactions. The reactivity of halopyridine substrates in homogeneous palladium-catalysed cross-coupling reactions was found to correlate with the binding strength between the zinc(II)-containing scaffolds and the corresponding halopyridine. Such observation is explained by the unfavourable formation of inactive over-coordinated halopyridine⋅⋅⋅palladium species. The presented approach is particularly appealing for those cases in which substrates and/or products deactivate (or partially poison) a transition-metal catalyst.

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“…Using a monometallic complex structure, the authors attained a styrene carbonate yield of 86%, at 318K and 4 MPa which corresponds to a TOF of 11.5h -1 , as well as, a styrene carbonate yield of 90%, at 318K and 1 MPa which corresponds to a TOF 12h -1 . In another work from the same group, Anselmo et al [35] reported the use of zinc complexes of bis-thiosemicarbazonato (btsc ligands). The authors attained a styrene carbonate conversion of 26% using a monometallic structure and TBAI as co-catalyst, at 318K and 1…”

Section: Resultsmentioning

confidence: 99%

Cyclic carbonate synthesis from CO2 and epoxides using zinc(II) complexes of arylhydrazones of β-diketones

Montoya

Gómez

Paninho

et al. 2016

Journal of Catalysis

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Zinc(II) complexes of arylhydrazones of β-diketones (AHBD) were used for the first time as catalysts combined with tetrabutylammonium bromide (TBABr), in the coupling reaction between CO 2 and epoxides. The influence of pressure and temperature on cyclic carbonate formation was investigated, as well as the catalytic activity towards different substrates (e.g. styrene oxide, propylene oxide and cyclohexene oxide). The molar ratio between metal complex and TBABr was determined for maximum catalytic activity.

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Mild formation of cyclic carbonates using Zn(II) complexes based on N2S2-chelating ligands

Cited by 27 publications

References 29 publications

Bis{μ-2,2′-[(butane-2,3-diylidene)bis(azanylylidene)]dibenzenethiolato}dizinc(II)–dimethyl sulfoxide–methanol (2/0.18/0.82)

Bis{μ-2,2′-[(butane-2,3-diylidene)bis(azanylylidene)]dibenzenethiolato}dizinc(II)–dimethyl sulfoxide–methanol (2/0.18/0.82)

Palladium‐Catalysed Cross‐Coupling Reactions Controlled by Noncovalent Zn⋅⋅⋅N Interactions

Cyclic carbonate synthesis from CO2 and epoxides using zinc(II) complexes of arylhydrazones of β-diketones

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