A homologous and homoleptic series of stable Group 11 metal triazenide complexes with the general formula [M(L')](n) (M = Cu or Au, n = 2; M = Ag, n = 3) featuring the bulky triazenide ligand N,N'-bis(2,6-di-isopropylphenyl)triazene, L'H, have been prepared by the reaction of Li[L'] with the metal chlorides, CuCl, AgCl, and [(THT)AuCl], respectively, in a 1:1 stoichiometric ratio. The compounds [Cu(2)(L')(2)] and [Au(2)(L')(2)] crystallized as dimers with M...M separations of 2.4458(4) A and 2.6762(4) A, respectively. In comparison, the reaction of AgCl with Li[L'] results in the formation of the tri-silver complex [Ag(3)(L')(3)] with Ag...Ag separations of 3.01184(17) A, 2.95329(17) A, and 2.92745(16) A. Attempts to react the parent triazene system L'H with [Cu(Mes)] resulted in the formation of the novel tri-copper system [Cu(3)(L')(2)(Mes)]. In all cases the molecular structures of the resultant complexes have been unambiguously determined by single crystal X-ray diffraction experiments.

A series of multinuclear Copper(I) guanidinate complexes have been synthesized in a succession of reactions between CuCl and the lithium guanidinate systems Li{L} (L = Me(2)NC((i)PrN)(2) (1a), Me(2)NC(CyN)(2) (1b), Me(2)NC((t)BuN)(2)(1c), and Me(2)NC(DipN)(2) (2d) ((i)Pr = iso-propyl, Cy = cyclohexyl, (t)Bu = tert-butyl, and Dip = 2,6-disopropylphenyl) made in situ, and structurally characterized. The di-copper guanidinates systems with the general formula [Cu(2){L}(2)] (L = {Me(2)NC((i)PrN)(2)} (2a), {Me(2)NC(CyN)(2)} (2b), and {Me(2)NC(DipN)(2)} (2d) differed significantly from related amidinate complexes because of a large torsion of the dimer ring, which in turn is a result of transannular repulsion between adjacent guanidinate substituents. Attempts to synthesis the tert-butyl derivative [Cu(2){Me(2)NC((t)BuN)(2)}(2)] result in the separate formation and isolation of the tri-copper complexes [Cu(3){Me(2)NC((t)BuN)(2)}(2)(μ-NMe(2))] (3c) and [Cu(3){Me(2)NC((t)BuN)(2)}(2)(μ-Cl)] (4c), both of which have been unambiguously characterized by single crystal X-ray diffraction. Closer inspection of the solution state behavior of the lithium salt 1c reveals a previously unobserved equilibrium between 1c and its starting materials, LiNMe(2) and N,N'-di-tert-butyl-carbodiimide, for which activation enthalpy and entropy values of ΔH(‡) = 48.2 ± 18 kJ mol(-1) and ΔS(‡) = 70.6 ± 6 J/K mol have been calculated using 1D-EXSY NMR spectroscopy to establish temperature dependent rates of exchange between the species in solution. The molecular structures of the lithium complexes 1c and 1d have also been determined and shown to form tetrameric and dimeric complexes respectively held together by Li-N and agostic Li···H-C interactions. The thermal chemistry of the copper complexes have also been assessed by thermogravimetric analysis.

The reaction of [(eta(5)-C(5)H(5))Cu(CNPh)] with phenyl-isocyanide results in an unprecedented double migratory insertion into two sp(2) C-H bonds of a eta(5)-coordinated cyclopentadienyl group, and formation of the 6-aminofulvene-2-aldimine complexes [(CNPh)Cu{kappa(2)-N,N-C(5)H(3)-1,2-(CHNPh)(2)}] and [(CNPh)(2)Cu{kappa(2)-N,N-C(5)H(3)-1,2-(CHNPh)(2)}], respectively, both of which have been structurally characterised.

We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structures of several cyclopentadienylcopper(I) isocyanide complexes have been unambiguously determined by single-crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η(5)-C5H5)Cu(CN(i)Pr)] (2a) and the tert-butyl isocyanide complex [(η(5)-C5H5)Cu(CN(t)Bu)] (2b) as possible copper metal chemical vapor deposition (CVD) precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et, and (i)Pr) has allowed the affect that these changes would have on features such as stability, volatility, and decomposition to be investigated. As part of this study, the vapor pressures of the complexes 2b, [(η(5)-MeC5H4)Cu(CN(t)Bu)] (3b), [(η(5)-EtC5H4)Cu(CN(t)Bu)] (4b), and [(η(5)-(i)PrC5H4)Cu(CN(t)Bu)] (5b) over a 40-65 °C temperature range have been determined. Low-pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b to synthesize thin films of metallic copper on silicon, gold, and platinum substrates under a H2 atmosphere. Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 and 300 °C by scanning electron microscopy and atomic force microscopy reveals temperature-dependent growth features: Films grown at 300 °C are continuous and pinhole-free, whereas films grown at 180 °C consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 °C shows a high degree of surface coverage with the formation of high-density, continuous, and pinhole-free thin films. Powder X-ray diffraction and X-ray photoelectron spectroscopy (XPS) both show the films to be high-purity metallic copper.

We report here a synthetic route to bis(N,N'-aryl)-6-aminofulvene-2-aldimine (AFA) ligand systems, specifically Ph(2)-AFAH and Dip(2)-AFAH. The synthesis and structural characterization of a series of Cu(I) complexes [(Ph(2)-AFA)Cu(CNPh)(2)] (2), [(Ph(2)-AFA)Cu(CN(i)Pr)] (3), and [(Dip(2)-AFA)Cu(CN(i)Pr)] (4), from the reaction of the corresponding lithiated AFA systems with Cu-Cl derivatives are reported; notably in the case of [(Ph(2)-AFA)Cu(CNPh)(2)] studies have revealed the existence of two structural isomers (2a and 2b), both of which can be isolated and structurally characterized. Density functional theory (DFT) calculations suggest that the two crystal forms are comparatively close in energy, and geometry optimization reveals a convergence of these two forms to a geometry that more closely resembles the solid-state structure of isomer 2b, having a CH···π interaction. The reactions of the AFA compounds Ph(2)-AFAH and Dip(2)-AFAH with ZnMe(2) and AlMe(3) have also been investigated, and the results of these reactions are described here.