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The α-diimine-ligated Zn-Zn-bonded compound [K(THF)][LZn-ZnL] (, L = [(2,6-PrCH)NC(Me)]) displays diverse reactivities toward a variety of ketones. In the reaction of with benzophenone or 4,4'-di--butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products and ). In contrast, treating with 9-fluorenone only afforded pinacolate complex . Moreover, the reactions of with N- or O-heterocycle-functionalized ketones, i.e., di(2-pyridyl)ketone, 2,2-pyrrolidinone, 9-xanthenone, or 10-methyl-9(10H)-acridone, were also carried out. Besides different transformations of the ketone moiety, the heteroatoms (nitrogen or oxygen) are also involved in coordination with zinc or potassium ions, yielding discrete aggregates or polymeric structures of products -.
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http://dx.doi.org/10.1021/acs.inorgchem.4c01669 | DOI Listing |
Inorg Chem
July 2024
Key Laboratory of Medicinal Molecule Science and Pharmaceutics Engineering, Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
The α-diimine-ligated Zn-Zn-bonded compound [K(THF)][LZn-ZnL] (, L = [(2,6-PrCH)NC(Me)]) displays diverse reactivities toward a variety of ketones. In the reaction of with benzophenone or 4,4'-di--butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products and ). In contrast, treating with 9-fluorenone only afforded pinacolate complex .
View Article and Find Full Text PDFInorg Chem
May 2022
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
This work provides a facile access to a series of triangular [ZnM] (M = group 10 and 11 metals) clusters. Treatment of Zn-Zn-bonded compounds [Zn-Zn] ( = CHC(2,6-PrCHN)CHC(CH)(NCHCHPR); R = Ph, Pr) with zero-valent transition-metal reagents selectively afforded the corresponding triangular clusters [ZnM], where M = Ni(0), Pd(0), and Pt(0). Notably, the isoelectronic triangular clusters [ZnM], where M = Ag(I) and Cu(I), could also be obtained by reactions of [LZn-ZnL] with AgOTf and CuOTf, respectively.
View Article and Find Full Text PDFNat Commun
October 2020
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032, Marburg, Germany.
The access to molecules comprising direct Zn-Zn bonds has become very topical in recent years for various reasons. Low-valent organozinc compounds show remarkable reactivities, and larger Zn-Zn-bonded gas-phase species exhibit a very unusual coexistence of insulating and metallic properties. However, as Zn atoms do not show a high tendency to form clusters in condensed phases, synthetic approaches for generating purely inorganic metalloid Zn units under ambient conditions have been lacking so far.
View Article and Find Full Text PDFChem Soc Rev
May 2012
Institut für Anorganische Chemie, Karlsruhe Institute of Technology, Engesserstrasse 15, 76131 Karlsruhe, Germany.
The discovery of decamethyldizincocene [Zn(2)(η(5)-Cp*)(2)] (Cp* = C(5)Me(5)), the first complex containing a covalent zinc-zinc bond, by Carmona in 2004 initiated the search for this remarkable class of compounds. Low-valent organozinc complexes can either be formed by ligand substitution reactions of [Zn(2)(η(5)-Cp*)(2)] or by reductive coupling reactions of Zn(ii) compounds. To the best of our knowledge, until now 25 low-valent Zn-Zn bonded molecular compounds stabilized by a variety of sterically demanding, very often chelating, organic ligands have been synthesized and characterized.
View Article and Find Full Text PDFChem Commun (Camb)
August 2011
Institut für Anorganische Chemie, Karlsruher Institut für Technologie, Engesserstr. 15, 76131 Karlsruhe, Germany.
The Zn-Zn bonded compound [(η(5)-Cp*)(2)Zn(2)] was investigated as catalyst for the inter- and intramolecular hydroamination reaction. High reaction rates under mild conditions were observed. This is the first application of a Zn-Zn bonded compound as catalyst.
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