Abstract
This review focuses on organotin compounds bearing hemicarbonate and carbonate ligands, and whose molecular structures have been previously resolved by single-crystal X-ray diffraction analysis. Most of them were isolated within the framework of studies devoted to the reactivity of tin precursors with carbon dioxide at atmospheric or elevated pressure. Alternatively, and essentially for the preparation of some carbonato derivatives, inorganic carbonate salts such as K2CO3, Cs2CO3, Na2CO3 and NaHCO3 were also used as coreagents. In terms of the number of X-ray structures, carbonate compounds are the most widely represented (to date, there are 23 depositions in the Cambridge Structural Database), while hemicarbonate derivatives are rarer; only three have so far been characterized in the solid-state, and exclusively for diorganotin complexes. For each compound, the synthesis conditions are first specified. Structural aspects involving, in particular, the modes of coordination of the hemicarbonato and carbonato moieties and the coordination geometry around tin are then described and illustrated (for most cases) by showing molecular representations. Moreover, when they were available in the original reports, some characteristic spectroscopic data are also given for comparison (in table form). Carbonato complexes are arbitrarily listed according to their decreasing number of hydrocarbon substituents linked to tin atoms, namely tri-, di-, and mono-organotins. Four additional examples, involving three CO2 derivatives of C,N-chelated stannoxanes and one of a trinuclear nickel cluster Sn-capped, are also included in the last part of the chapter.
Highlights
Over the past fifty years, the coordination of CO2 on metal centers has aroused great interest, mobilizing numerous groups around the world; even today, it continues to fascinate the community of inorganic and organometallic chemists
The zinc-based active site of carbonic anhydrase has been widely used as a model for the design of metal complexes in order to mimic the catalytic role of the enzyme toward carbon dioxide [6]
The authors claimed that alkaline reaction conditions (20% ammonia aqueous five-coordinated and display a trigonal bipyramidal (TBP) geometry in which equatorial positions are occupied by phenyls solution) promote the capture of atmospheric CO22, leading to carbonato triorganotins 12 and 13
Summary
Over the past fifty years, the coordination of CO2 on metal centers has aroused great interest, mobilizing numerous groups around the world; even today, it continues to fascinate the community of inorganic and organometallic chemists. Pioneering works in this area are to be credited to M. These two distinct families of compounds are successively detailed on hemicarbonato and carbonato tin derivatives These two distinct families of compounds are thereafter, with a particular focus upon syntheticfocus and structural. Thishypervalence inventory highlights the hypervalence of tin atoms in hemicarbonate and carbonate derivatives, adopt pentaand hexa-coordination modes, with trigonal bipyramidal and octahedral geometries, which preferentially adopt penta- and hexa-coordination modes, with trigonal bipyramidal and respectively.
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