Abstract:Copper(I) [Cu 2 (μ-Br) 2 ( t BuImCH 2 pyCH 2 L)] n (L = OMe, NEt 2 , NH t Bu) compounds supported by flexible functionalized NHC-based polydentate ligands have been prepared in a one-pot procedure by reacting the corresponding imidazolium salt with an excess of copper powder and Ag 2 O. An X-ray diffraction analysis has revealed that [Cu 2 (μ-Br) 2 ( t BuImCH 2 pyCH 2 NEt 2 )] n is a linear coordination polymer formed by bimetallic [Cu(μ-Br)] 2 units linked by the lutidine-based NHC-py-NEt 2 ligand, which acts… Show more
“…15 Further support for mechanism was provided by the isolation and characterization of dicopper σ,π-alkynyl intermediates. 15,16 We have recently been comparing 'soft' thiolate-(L 1 ) and 'hard' amido-(L 2 ) SNS ligands (Schemes 2 and 3) in ligandassisted catalysis. 17,18 Working with base metals from Mn to Zn we demonstrated several different bifunctional mechanisms for catalysed hydroboration [19][20][21][22][23] and hydrosilylation 24 of carbonyls, nitriles 25,26 and N-heterocycles.…”
Two tetranuclear Cu(I) complexes bearing thiolate- and amido-SNS ligands were characterized by X-ray diffraction and mass spectrometry. Although the amido ligand undergoes irreversible N-protonation by the copper-bound alkyne, the thiolate...
“…15 Further support for mechanism was provided by the isolation and characterization of dicopper σ,π-alkynyl intermediates. 15,16 We have recently been comparing 'soft' thiolate-(L 1 ) and 'hard' amido-(L 2 ) SNS ligands (Schemes 2 and 3) in ligandassisted catalysis. 17,18 Working with base metals from Mn to Zn we demonstrated several different bifunctional mechanisms for catalysed hydroboration [19][20][21][22][23] and hydrosilylation 24 of carbonyls, nitriles 25,26 and N-heterocycles.…”
Two tetranuclear Cu(I) complexes bearing thiolate- and amido-SNS ligands were characterized by X-ray diffraction and mass spectrometry. Although the amido ligand undergoes irreversible N-protonation by the copper-bound alkyne, the thiolate...
“…Recently, the coordination of several CuAAC catalysts to small molecule substrates has been evaluated using density functional theory. 44–46 Overall, and surprisingly independent of the catalyst used, the studies agreed that the coordination distance of the azide moiety to the pre-formed alkyne-catalyst complex is just above 0.2 nm. This was used as a guideline for the current study, in which we assumed that distances between the polymer termini of below 1 nm would favour intra-molecular CuAAC reaction.…”
The synthesis of cyclic polymers has made tremendous progress over the last decade. However, upscaling remains a challenge. To achieve acceptable cyclization yields, time, and labour intensive screening of experimental...
“…Such species are proposed in catalytic dinuclear models for the CuAAC reactions, previously established in the literature as one of the possible pathways. 24…”
Section: Resultsmentioning
confidence: 99%
“…22 As a representative example of the development of nitrogen-based ligands toward CuAAC reactions, Tilley and co-workers, isolated a series of dinuclear copper( i ) intermediates using the dinucleating ligand 2,7-bis(fluoro-di(2-pyridyl)-methyl)-1,8-naphthyridine (Chart 1, D ), 23 which supported the propensity of catalytic dinuclear species in CuAAC reactions, with cooperation between the two copper centers. 24 When considering neutral dinuclear copper( i ) complexes, several examples of their preparation and structural characterization are to be noted, the vast majority utilizing monoanionic ligand systems such as amidinates (X = CR) or guanidinates (X = N) (Chart 1, E ). 25…”
Five dinuclear copper(I) complexes of the type [Cu{κN,κN’-5-R-NC4H2-2-C(H)=N(2,6-iPr2C6H3)}]2 (1a-e; R = 2,4,6-iPr3C6H2 (a), R = 2,6-Me2C6H3 (b), R = 3,5-(CF3)2C6H3 (c), R = 2,6-(MeO)2C6H2 (d), R = CPh3 (e)) were...
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