The chemistry of β-diketonate copper(I) compounds—III. The synthesis of (β-diketonate) Cu(1,5-COD) compounds, the solid state structure and disproportionation of hexafluoroacetylacetonato (1,5-cyclooctadiene)copper(I), (hfac)Cu(1,5-COD)

The chemistry of copper(I) β-diketonate compounds. Part V. Syntheses and characterization of (β-diketonate)CuLn species where L = PBu3, PPh3, and PCy3; n = 1 and 2; crystal and molecular structures of (acac)Cu(PCy3), (tfac)Cu(PCy3), (hfac)Cu(PCy3), and (hfac)Cu(PCy3)2

“…However, no trends in C u 4 bond distances between the compounds can be discerned, within the limits of error on the data, that would clearly enable a comparison of thermodynamic parameters such as bond length -bond strength relationships as a function of the Pdiketonate substituents. The bite angles of the P-diketonate ligands -91"--94" and the C u 4 bond lengths of -2.00 A are similar to other copper(1) P-diketonate complexes bearing one Lewis base adduct (8,28,32,33). Similarly, no unambiguous trends in Cu-P bond lengths or C 4 and C -C bond lengths and angles, within the limits of error of the data, were observed that would enable comparison to the spectroscopic trends observed.…”

“…The compounds (P-diketonate)CuL that were characterized previously were shown to be monomeric in the solid state and in solution (8,28,32,33), and thus the (Pdiketonate)Cu(PR,) complexes described here were expected to exhibit a similar trigonal-planar arrangement of ligands about the central copper(1) atom. The species (P-diketonate)Cu(PR& were expected to be monomeric, four-coordinate, and tetrahedral by comparison to the literature data for analogous complexes, assuming that the Pdiketonate ligand remains chelating (22,25 …”

“…However, the result of a proton NMR study in which pyridine-d, was reacted with (hfac)CuPMe, revealed that addition of one drop of pyridined, to a benzene-d, solution of (hfac)CuPMe, caused the 'H resonance of the coordinated PMe, to be deshielded by 0.4 1 ppm, and dissolution of (hfac)CuPMe, in pyridine-dj resulted in further deshielding of 0.72 ppm. We previously observed that the coordination of the Lewis bases to the copper(1) center is dominated by the a-donor ability, not the .rr-acceptor ability, as evidenced by the small change in carbon-carbon bond lengths of olefin and alkyne ligands on coordination to the (P-diketonate)Cu(I) moiety (8,32).…”

“…111) (7)(8)(9) over a temperature range 80-400°C and, in some cases, deposit copper selectively (7)(8)(9)(10)(11)(12)(13)(14)(15). Selective copper deposition from (P-diketonate)CuL compounds onto the metals Pt, W, and Cu in the presence of SiO, and the minimum deposition temperature are strongly influenced by the nature of the P-diketonate substituents and Lewis base ligands, L. For example, (hfac)CuPMe, selectively deposits copper onto W and not SiO, in the temperature range 150-300°C.…”

Impact of Group 10 Metals on the Solvent‐Induced Disproportionation of o‐Semiquinonato Complexes

“…For example, the Cu I center in [Cu(acac)(NH 3 ) 2 ] (acac=acetylacetonato) spontaneously disproportionates into metallic Cu 0 and [Cu II (acac) 2 ] in liquid NH 3 . Hampden‐Smith and co‐workers have also reported that [Cu I (β‐diketonato)(cod)] (cod=cyclooctadiene) thermally disproportionates into metallic Cu 0 and [Cu II (β‐diketonato) 2 ] at temperatures in excess of 200 °C . Furthermore, Matsumoto and co‐workers have reported tetranuclear Pt II 2 Pt III 2 complexes of the type [Pt II Pt III (NH 3 ) 4 (C 4 H 6 NO) 2 ] 2 6+ , which disproportionate into [Pt III 2 (NH 3 ) 4 (C 4 H 6 NO) 2 LL′] 4+ (L, L′=H 2 O, OH − , or SO 4 2− ) and [Pt II 2 (NH 3 ) 4 (C 4 H 6 NO) 2 ] 2+ under acidic conditions .…”