The efficiency of the deprotonated aryl bis-sulfone [2,6-{(p-tolyl)SO2}2C6H3](-) as an O,C,O-coordinating pincer-type ligand was described. The bis-sulfone precursor was synthesized using a straightforward palladium-catalyzed cross-coupling reaction. As a result of directed ortho metalation (DoM) through sulfonyl groups, a selective lithiation of the aryl group was achieved and the corresponding carbanion was isolated and its structure determined by single-crystal X-ray diffraction analysis. A heteroleptic tin(II) complex has been prepared by a nucleophilic substitution reaction. Crystallographic analysis and DFT calculations indicate that the bis-sulfonyl moiety acts as a new O,C,O-coordinating pincer-type ligand with intramolecular S=O coordination to a tin(II) center. The cis form with the two nonbonded oxygen atoms of the sulfonyl groups on the same side is preferentially obtained.
The reactivity of amidinate (1a,b, 2a)-or NHC (5a,b)-stabilized germanium(II) compounds toward diiron nonacarbonyl has been investigated. These germylenes act as two-electron carbene-like ligands and lead to stable germylene iron complexes by exchange reaction of a carbonyl ligand. Whereas the amidinato chloro germylenes lead to stable complexes, a bis(iron germylene) oxide was obtained from the bis-amidinato germylene. The reactions of NHC-stabilized germylenes (5a,b) with Fe 2 (CO) 9 were also explored, giving donor−acceptor complexes of germylenes. All the germanium−iron complexes were fully characterized ( 1 H and 13 C NMR and IR) including by single-crystal X-ray diffraction structure determinations.
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