The Presence of [Ar<sub>2</sub>Cu]<sup>-</sup> and [(RC⋮C)<sub>2</sub>Cu]<sup>-</sup>\nHomocuprate Moieties in the Neutral Mixed Cuprate\n[Cu<sub>2</sub>Li<sub>2</sub>(C⋮CR)<sub>2</sub>Ar<sub>2</sub>] (Ar =\nC<sub>6</sub>H<sub>4</sub>{CH<sub>2</sub>N(Me)CH<sub>2</sub>CH<sub>2</sub>NMe<sub>2</sub>}-2; R = C<sub>6</sub>H<sub>4</sub>Me-4 or\nC<sub>6</sub>H<sub>4</sub>SiMe<sub>3</sub>-4)
Claudia M. P. Kronenburg (2418391)Johann T. B. H. Jastrzebski (1234875)Martin Lutz (1234866)Anthony L. Spek (1913542)Gerard van Koten (1589131)
Abstract
The neutral, mixed 2:2 aryl-alkynyl-cuprates [Cu<sub>2</sub>Li<sub>2</sub>(C⋮CR)<sub>2</sub>Ar<sub>2</sub>] (Ar = [C<sub>6</sub>H<sub>4</sub>{CH<sub>2</sub>N(Me)CH<sub>2</sub>CH<sub>2</sub>NMe<sub>2</sub>}-2]<sup>-</sup>; R = C<sub>6</sub>H<sub>4</sub>Me-4 (<b>3a</b>) or C<sub>6</sub>H<sub>4</sub>SiMe<sub>3</sub>-4 (<b>3b</b>)) are the first examples of cuprates\nthat contain two different organic homocuprate parts ([Ar−Cu−Ar]<sup>-</sup> and [(RC⋮C)−Cu−(C⋮CR)]<sup>-</sup>) in one assembled structure. Each part has a two-coordinate Cu atom in linear\ngeometry. They are held together by Li−C<sub>ipso</sub> interactions to two Li atoms. Tetrahedral four-coordination at the Li centers is completed by N,N‘-chelation of the <i>ortho</i>-diamine substituent\nof the Ar ligand. Compound <b>3</b> is formed as the only reaction product in almost quantitative\nyield when LiAr and Cu(C⋮CR) aggregates are mixed together in equimolar amounts. This\ncuprate is an example of ion-pairing between two different homocuprate anions and two Li\ncations.
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