Wydział Chemii

Kamil Sokołowski

Wojciech Bury

Adam Tulewicz

Anna M. Cieślak

Iwona Justyniak

Dominik Kubicki

Elżbieta Krajewska

Anne Milet

Robert Moszyński

Janusz Lewiński

2015

Chemistry-A European Journal

21

5496-5503

10.1002/chem.201406271

Naukowa

Angielski

Artykuł

Organozinc hydroxides, RZnOH, possessing the proton-reactive alkylzinc group and the CO2-reactive Zn OH group, represent an intriguing group of organometallic precursors for the synthesis of novel zinc carbonates. Comprehensive experimental and computational investigations on 1) solution and solid-state behavior of tBuZnOH (1) species in the presence of Lewis bases, namely, THE and 4-methylpyridine; 2) step-by-step sequence of the reaction between / and CO2; and 3) the effect of a donor ligand and/or an excess of tBu(2)Zn as an external proton acceptor on the reaction course are reported. DFT calculations for the insertion of carbon dioxide into the dinuclear alkylzinc hydroxide 12 are fully consistent with H-1 NMR spectroscopy studies and indicate that this process is a multistep reaction, in which the insertion of CO2 seems to be the rate-determining step. Moreover, DFT studies show that the mechanism of the rearrangement between key intermediates, that is, the primary alkylzinc bicarbonate with a proximal position of hydrogen and the secondary alkylzinc bicarbonate with a distal position of hydrogen, most likely proceeds through internal rotation of the dinuclear bicarbonate.

carbon dioxide fixation, computational chemistry, density functional calculations, reaction mechanisms, zinc, zinc hydroxide

http://dx.doi.org/10.1002/chem.201406271

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