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Well-defined coinage metal transfer agents for the synthesis of NHC-based nickel, rhodium and palladium macrocycles
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Andrew, Rhiann, Storey, Caroline M. and Chaplin, Adrian B. (2016) Well-defined coinage metal transfer agents for the synthesis of NHC-based nickel, rhodium and palladium macrocycles. Dalton Transactions, 45 (21). pp. 8937-8944. doi:10.1039/c6dt01263a
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Official URL: http://dx.doi.org/10.1039/C6DT01263A
Abstract
With a view to use as carbene transfer agents, well-defined silver(I) and copper(I) complexes of a macrocyclic NHC-based pincer ligand, bearing a central lutidine donor and a dodecamethylene spacer [CNC–(CH2)12, 1], have been prepared. Although the silver adduct is characterised by X-ray diffraction as a dinuclear species anti-[Ag(μ-1)]22+, variable temperature measurements indicate dynamic structural interchange in solution involving fragmentation into mononuclear [Ag(1)]+ on the NMR time scale. In contrast, a mononuclear structure is evident in both solution and the solid-state for the analogous copper adduct partnered with the weakly coordinating [BArF4]− counter anion. A related copper derivative, bearing instead the more coordinating cuprous bromide dianion [Cu2Br4]2−, is notable for the adoption of an interesting tetranuclear assembly in the solid-state, featuring two cuprophilic interactions and two bridging NHC donors, but is not retained on dissolution. Coinage metal precursors [M(1)]n[BArF4]n (M = Ag, n = 2; M = Cu, n = 1) both act as carbene transfer agents to afford palladium, rhodium and nickel complexes of 1 and the effectiveness of these precursors has been evaluated under equivalent reaction conditions.
| Item Type: | Journal Article | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||||||
| Divisions: | Faculty of Science > Chemistry | ||||||||
| Library of Congress Subject Headings (LCSH): | Carbenes (Methylene compounds), Organometallic chemistry, Catalysis | ||||||||
| Journal or Publication Title: | Dalton Transactions | ||||||||
| Publisher: | Royal Society of Chemistry | ||||||||
| ISSN: | 1477-9226 | ||||||||
| Official Date: | 9 May 2016 | ||||||||
| Dates: |
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| Date of first compliant deposit: | 16 August 2016 | ||||||||
| Volume: | 45 | ||||||||
| Number: | 21 | ||||||||
| Page Range: | pp. 8937-8944 | ||||||||
| DOI: | 10.1039/c6dt01263a | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Open Access | ||||||||
| Funder: | University of Warwick, European Research Council (ERC), Royal Society (Great Britain) | ||||||||
| Grant number: | grant agreement 637313 (ERC) |
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