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Synthesis and Comparison of Transition Metal Complexes of Abnormal and Normal Tetrazolylidenes: A Neglected Ligand Species

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posted on 17.06.2013, 00:00 by Lars-Arne Schaper, Xuhui Wei, Philipp J. Altmann, Karl Öfele, Alexander Pöthig, Markus Drees, János Mink, Eberhardt Herdtweck, Bettina Bechlars, Wolfgang A. Herrmann, Fritz E. Kühn
To date, only few examples of tetrazolylidene carbenes coordinated to transition metal complexes have been described. A direct comparison of “normal” tetrazolylidenes (1,4-substitution pattern) and “abnormal” tetrazolylidenes (also referred to as “mesoionic carbenes”; 1,3-substitution pattern) has not been performed at all. In this work, we describe coordination of both ligand types to a row of transition metals. For example, the first examples of tetrazolylidene Mo, Ag, or Ir complexes have been isolated and fully characterized. The mesoionic tetrazolylidene Ag compound 2d is shown to be a viable carbene transfer reagent. By means of NMR, IR, and Raman spectroscopy, as well as X-ray crystallography and computational results, the pronounced differences between the two ligand substitution patterns are highlighted. It is shown that simply changing the position of a methyl group from N3 to N4 in the heterocycle can cause enormous differences in ligand characteristics.

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