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Relevant academic research and scientific papers

Monomeric Alkoxo Complexes of Copper(I): Syntheses and Structures of Di(p-tolylisocyanide)(2,6-di-t-butylphenoxo)copper(I) and a Di(2,6-dimethylphenoxo)cuprate(I)

Copper(I) chloride reacts with 2,6-But2C6H3ONa in the presence of p-MeC6H4NC to give t2C6H3O)> containing a tri-coordinated copper(I) atom , while the solution obtained from 'CuCOCl' and 2,6-Me2C6H3ONa reacts with PhCH=N-CH2CH2-N=CHPh, BEN, to give the diphenoxocuprate(I) +- .

Copper(I)-phenoxide complexes: Synthesis and ligand-induced transformations of the copper(I)-phenoxo functionality

Synthesis and structural characteristics of copper(I) complexes containing the [Cu-OAr] unit are reported. Ancillary ligands promote transformations into the various forms in which this unit occurs. These forms are closely related to those found in copper(I)-alkyl and -aryl chemistry. Reaction of copper(I) chloride with sodium phenoxides, NaOAr (Ar = Ph, 2,6-Me2C6H3), under nitrogen in THF, gave solutions of Cu(I) phenoxides (I) that rapidly decomposed to copper metal. The same reaction under carbon monoxide, however, gave the compounds [S(CO)Cu(μ-OAr)2Cu(CO)S] (II) (S = THF; Ar = Ph, 2,6-Me2C6H3). By addition of monodentate ligands, L, to solutions of II, the complexes [L2Cu(μ-OAr)2CuL2] (III) (L = PPh3, p-MeC6H4NC; Ar = Ph) crystallized (ν(C-N): 2145 and 2125 cm-1). The solid-state structure (L = p-MeC6H4NC) showed a close proximity of the two copper(I) atoms (Cu?Cu = 3.223 (1) A?), Cu-O bond distances of 2.066 (4) and 2.083 (4) A?, and a tetrahedral coordination around copper(I) as expected. By use of a tridentate ligand, the phenoxo group was forced to display a terminal bonding mode in [Cu(TRIPHOS)(OPh)] (V). The same result was achieved by using bulky substituents at the phenyl ring of the phenoxo group in [Cu(p-MeC6H4NC)2(2,6-t-Bu2C 6H3O)] (VIII) (ν(C-N) (Nujol): 2145 and 2170 cm-1). Bidentate ligands, in turn, caused the rearrangements of the bimetallic unit [Cu2(μ-OAr)2]. The ligand BEN (BEN = N,N′-ethylenebis(benzaldimine)), upon reaction with a solution of II (Ar = 2,6-Me2C6H3), promoted a ligand disproportionation leading to the phenoxo-cuprate(I) complex [Cu(BEN)2]+[ArO-Cu-OAr]- (VII) (Ar = 2,6-Me2C6H3), the structure of which was determined by X-ray analysis. The cuprato anion has a linear coordination (O-Cu-O = 169.8 (3)°) with short Cu-O bond distances (1.806 (6), 1.798 (8) A?). The reaction of dppe with a solution of II (Ar = Ph), however, gave the dinuclear compound [[Cu(OPh)(dppe)]2(μ-dppe)]·4THF (VI), containing terminal phenoxo ligands (Cu-O = 2.023 (5) A?). This compound may be an intermediate through which the rearrangement of II occurs in the reaction with BEN. The Cu-O bond distance was found to increase as the coordination number of Cu(I) increased from 2 (VIII; Cu-O = 1.806 (6) A?) to 3 (III, L = p-MeC6H4NC; Cu-O = 1.917 (3) A?) to 4 (VI; Cu-O = 2.023 (5) A?). Crystallographic details for complex III (L = p-MeC6H4NC): space group P21/n (monoclinic); a = 11.288 (3), b = 10.374 (3), c = 16.449 (4) A?; β = 95.62 (3)°; V = 1917.0 (9) A?3; Z = 2; Dcalcd = 1.35 g cm-3. The final R factor was 0.052 (Rw = 0.059) for 1932 observed reflections. Crystallographic details for complex VIII; space group P21/n (monoclinic); a = 23.179 (4), b = 9.456 (1), c = 12.509 (2) A?; β = 94.02 (2)°; V = 2735.0 (7) A?3; Z = 4; Dcalcd = 1.22 g cm-3. The final R factor was 0.039 (Rw = 0.043) for 2623 observed reflections. Crystallographic details for complex VI; space group Pbca (orthorhombic); a = 23.524 (7), b = 21.746 (6), c = 18.572 (4) A?; V = 9501 (4) A?3; Z = 4; Dcalcd = 1.26 g cm-3. The final R factor was 0.049 (Rw = 0.057) for 3837 observed reflections. Crystallographic details for complex VII: P21/c (monoclinic); a = 13.643 (3), b = 21.528 (5), c = 15.538 (4) A?; β = 111.31 (3)°; V = 4252 (2) A?3; Z = 4; Dcalcd = 1.32 g cm-3. The final R factor was 0.042 for 2410 observed reflections.