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Hoffmann, R. A wiki for the life sciences where authorship matters. Nature Genetics (2008)

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Evans, W.J. et al.

Evans, Miller, Ziller,

Synthesis of (O(2)CEPh)(1)(-) Ligands (E = S, Se) by CO(2) Insertion into Lanthanide Chalcogen Bonds and Their Utility in Forming Crystallographically Characterizable Organoaluminum Complexes [Me(2)Al(mu-O(2)CEPh)](2).

CO(2) inserts into the Sm-S and Sm-Se bonds of [(C(5)Me(5))(2)Sm(mu-EPh)](2) (E = S, Se) to form the first crystallographically characterized (O(2)CEPh)(1)(-) complexes, [(C(5)Me(5))(2)Sm(mu-O(2)CEPh)](2). These complexes are structurally analogous to [(C(5)Me(5))(2)Sm(mu-O(2)CR)](2) complexes, but they are less soluble. This feature was utilized in the reaction of Me(2)AlCl with [(C(5)Me(5))(2)Sm(mu-O(2)CEPh)](2), which forms crystallographically characterizable [Me(2)Al(mu-O(2)CEPh)](2) complexes. Such complexes could not be isolated from an analogous carboxylate reaction. [(C(5)Me(5))(2)Sm(mu-O(2)CSePh)](2) decarboxylates in THF to form (C(5)Me(5))(2)Sm(SePh)(THF). The loss of CO(2) rather than COSe with formation of (C(5)Me(5))(2)Sm(OPh)(THF) was established by (13)CO(2) studies and independent synthesis of (C(5)Me(5))(2)Sm(OPh)(THF) from (C(5)Me(5))(2)Sm[N(SiMe(3))(2)] and PhOH.[1]

References

Synthesis of (O(2)CEPh)(1)(-) Ligands (E = S, Se) by CO(2) Insertion into Lanthanide Chalcogen Bonds and Their Utility in Forming Crystallographically Characterizable Organoaluminum Complexes [Me(2)Al(mu-O(2)CEPh)](2). Evans, W.J., Miller, K.A., Ziller, J.W. Inorganic chemistry. (2006) [Pubmed]

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