Comproportionation Synthesis of Copper(I) Alkynyl Complexes Encapsulating Polyoxomolybdate Templates: Bowl-Shaped Cu33 and Peanut-Shaped Cu62 Nanoclusters

Comproportionation reaction of Cu­(II) salt and copper metallic powder in the presence of tert-butylacetylene (tBuCCH) in methanol at room temperature yielded discrete Cu­(I) tert-butylethynide clusters whose identity depended on the particular co-existing anion employed. Introduction of polyoxomol...

Full description

Saved in:
Bibliographic Details
Published inJournal of the American Chemical Society Vol. 138; no. 9; pp. 2909 - 2912
Main Authors Zhang, Li-Min, Mak, Thomas C. W
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 09.03.2016
Online AccessGet full text

Cover

More Information
Summary:Comproportionation reaction of Cu­(II) salt and copper metallic powder in the presence of tert-butylacetylene (tBuCCH) in methanol at room temperature yielded discrete Cu­(I) tert-butylethynide clusters whose identity depended on the particular co-existing anion employed. Introduction of polyoxomolybdate to the reaction system afforded two new core–shell nanoclusters, [Cu33(tBuCC)24(Mo4O16)]·BF4 (3) and [Cu62(tBuCC)34(Mo5O19)2(MoO4)2(OTf)2(OH)4]·(OTf)2 (4). Complexes 3 and 4 represent the first examples of high-nuclearity Cu­(I) clusters that encapsulate polyoxometalate templates, and the latter features the largest Cu­(I) alkynyl cluster known to date. The present study not only demonstrates a new paradigm for the designed synthesis of Cu­(I) alkynyl clusters but also opens the door to understanding Cu­(I) alkynyl structural chemistry.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b12103