Syntheses, Structures, and Thermal Behavior of Cu(hfacac) Complexes Derived from Ethanolamines

Abstract

A series of novel precursors for MOCVD of metallic copper have been synthesized and structurally characterized. These precursors are composed of Cu(hfacac)(2), which serves as a volatile source of Cu, and amino alcohols, which act as reductants and anchor firmly to the copper center through the amine unit. In some cases, a proton transfer from the coordinated alcohol to the hfacac ligand results in the formation of an alkoxide unit and the release of the free Hhfacac. Metallic copper films can be deposited by MOCVD at 300 degrees C without any external reductant. Crystal data: Cu(hfacac)(2).C(7)H(8) (-103 degrees C), a = 6.510(6) Å, b = 8.594(7) Å, c = 18.478(15) Å, orthorhombic space group Pmnn, Z = 2; Cu(hfacac)(2)(H(2)NCH(2)CH(2)OH) (-158 degrees C), a = 13.145(1) Å, b = 13.418(1) Å, c = 11.245(1) Å, alpha = 110.39(1) degrees, beta = 99.12(1) degrees, gamma = 97.90(1) degrees, triclinic space group P&onemacr;, Z = 4; [Cu(hfacac)(Me(2)NCH(2)CH(2)O)](2) (-153 degrees C), a = 9.259(2) Å, b = 12.011(3) Å, c = 6.304(1) Å, alpha = 91.19(1) degrees, beta = 106.66(1) degrees, gamma = 74.83(1) degrees, triclinic space group P&onemacr;, Z = 1; Cu(hfacac)[N(CH(2)CH(2)OH)(2)(CH(2)CH(2)O)].MeOH (-168 degrees C), a = 10.075(4) Å, b = 8.611(4) Å, c = 19.259(9) Å, beta = 99.82(2) degrees, monoclinic space group P2(1)/m, Z = 4.

Synthesis and Characterisation of the First Oxazoline Coordination Compounds Containing the Cu(F6acac)2 Unit: X-ray Diffraction Studies of Cu(kappa2-O,O'-F6acac)2(kappa1-N-Meox) and Cu(kappa2-O,O'-F6acac)2(kappa1-N-Etox)

“…[13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][33][34][35] As expected, the complexes reported herein contain chelating κ 2 -O,O'-bonded F 6 acac formally anionic groups with Cu-O bond lengths which are of the typical range (1.9-2.2 Å). The oxazoline ligand, predictably N-bonded, 4,5,[7][8][9][10][11][12]31 occupies a basal position with one of the F 6 acac O-atoms occupying the formal equatorial position of an idealised square pyramidal ligand arrangement.…”

“…This copper containing starting material has been extensively studied in coordination chemistry and materials science due to its ability to coordinate a variety of N-donor ligands which includes organic radicals, heterocycles, primary amines, etc. A wide variety of structural bonding motifs [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] have been observed in the resulting coordination compounds. …”

Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

“…The binding of the H 2 tea ligand involves the chelate [38] It coordinates the metal with a Cu À N2 À N3 angle of 118.45(10)8. For 1 most of the bond distances are similar to those of related triethanolaminate complexes of copper such as [Cu(H 2 tea)Cl], [36] [Cu(H 2 tea)NCS], [36] [Cu 2 (H 2 tea) 2 (4,4'-bipy)](ClO 4 ) 2 [37] and [Cu(H 2 tea)-(CF 3 COCHCOCF 3 )] [39] . The molecular structure of 2c consists of centrosymmetric binuclear fragments [Cu 2 (H 2 tea) 2 ] 2 þ stabilized by two monodentate 3-chlorobenzoate ligands (Figure 3), which are further involved in an intermolecular hydrogen bonding network with non-coordinated water molecules, thus forming parallel chains in neighbouring layers ( Figure 4).…”

Copper and calcium complexes with the anionic O2-donor 4-tert-butylacetyl-3-methyl-1-phenylpyrazol-5-onato (Q−). Influence of hydrogen-bond interactions on lattice architecture in the crystal structures of [CuQ2(H2O)] and [CaQ2(EtOH)2]

“…acetylacetonate (1.92 Å), 45 benzoylacetonate (1.91-1.93 Å), 46 and hexafluoroacetylacetonate (1.911 Å). 47 The water molecule occupies the apex in the pyramid, with Cu-O distance 2.25 Å. A description as a five-co-ordinated species can be made in terms of the distance ρ (Å) from copper to the average plane of the four ligands.…”