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Experimental and Computational Insights into Carbon Dioxide Fixation by RZnOH Species
Author(s) -
Sokołowski Kamil,
Bury Wojciech,
Tulewicz Adam,
Cieślak Anna M.,
Justyniak Iwona,
Kubicki Dominik,
Krajewska Elżbieta,
Milet Anne,
Moszyński Robert,
Lewiński Janusz
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406271
Subject(s) - chemistry , bicarbonate , carbon fixation , insertion reaction , hydroxide , ligand (biochemistry) , carbon dioxide , inorganic chemistry , organic chemistry , catalysis , biochemistry , receptor
Organozinc hydroxides, RZnOH, possessing the proton‐reactive alkylzinc group and the CO 2 ‐reactive ZnOH 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 t BuZnOH ( 1 ) species in the presence of Lewis bases, namely, THF and 4‐methylpyridine; 2) step‐by‐step sequence of the reaction between 1 and CO 2 ; and 3) the effect of a donor ligand and/or an excess of t Bu 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 1 2 are fully consistent with 1 H NMR spectroscopy studies and indicate that this process is a multistep reaction, in which the insertion of CO 2 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.