Synthesis and Comparison of Transition Metal Complexes of Abnormal and Normal Tetrazolylidenes: A Neglected Ligand Species
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- 作者：Lars-Arne Schaper ; Xuhui Wei ; Philipp J. Altmann ; Karl 脰fele ; Alexander P枚thig ; Markus Drees ; J谩nos Mink ; Eberhardt Herdtweck ; Bettina Bechlars ; Wolfgang A. Herrmann ; Fritz E. K眉hn
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：June 17, 2013
- 年：2013
- 卷：52
- 期：12
- 页码：7031-7044
- 全文大小：641K
- 年卷期：v.52,no.12(June 17, 2013)
- ISSN：1520-510X
文摘
To date, only few examples of tetrazolylidene carbenes coordinated to transition metal complexes have been described. A direct comparison of 鈥渘ormal鈥?tetrazolylidenes (1,4-substitution pattern) and 鈥渁bnormal鈥?tetrazolylidenes (also referred to as 鈥渕esoionic carbenes鈥? 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.