Synthesis and characterization of (.beta.-diketonato)copper(I) alkyne complexes: structural characterization of (hexafluoroacetylacetonato)(diphenylacetylene)copper(I)

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).…”

Facile Syntheses of Copper(I) Alkynyl Clusters Stabilized by Hexafluoroacetylacetonate (hfac) Ligands: The Structure of [Cu26(hfac)11(1-pentynyl)15] This work was supported by Avecia, Seiko-Epson Corporation, and EPSRC funding. We would like to thank Stephen Boyer of the Computing and Engineering Department of the University of North London for performing microanalyses. We would also like to thank Dr. Mary McPartlin for a stimulating discussion with regard to interpretation of our crystallographic results.

“…Therefore, these closed shell interactions in the [Cu 26 (hfac) 11 (1‐pentynyl) 15 ] cluster make only a minor contribution to defining its primary structure 37. The hfac‐capped Cu atoms all have near‐planar O 2 C 2 donor‐sets with hfac chelate ring dimensions similar to those in other Cu I complexes 38. 39…”

Facile Syntheses of Copper(I) Alkynyl Clusters Stabilized by Hexafluoroacetylacetonate (hfac) Ligands: The Structure of [Cu26(hfac)11(1-pentynyl)15] This work was supported by Avecia, Seiko-Epson Corporation, and EPSRC funding. We would like to thank Stephen Boyer of the Computing and Engineering Department of the University of North London for performing microanalyses. We would also like to thank Dr. Mary McPartlin for a stimulating discussion with regard to interpretation of our crystallographic results.

“…Therefore, these closed shell interactions in the [Cu 26 (hfac) 11 (1-pentynyl) 15 ] cluster make only a minor contribution to defining its primary structure. [38,39] The simplicity of the preparation of these clusters and the range of nuclearities obtained is remarkable. [38,39] The simplicity of the preparation of these clusters and the range of nuclearities obtained is remarkable.…”