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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

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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, Engineering and Medicine > 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:
DateEvent
9 May 2016Published
27 April 2016Accepted
UNSPECIFIEDSubmitted
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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