Australian Journal of Chemistry
Volume 69 Number 5 2016
Professor Brice Bosnich In Memoriam
CH15433Antimicrobial Properties of Mono- and Di-fac-rhenium Tricarbonyl 2-Pyridyl-1,2,3-triazole Complexes
A family of mono- and di-fac-rhenium tricarbonyl 2-pyridyl-1,2,3-triazole complexes with different aliphatic and aromatic substituents were synthesized in good-to-excellent yields. The complexes were tested for antimicrobial activity in vitro against both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) microorganisms. Several of the cationic complexes displayed activity against Staphylococcus aureus, but the minimum inhibitory concentrations for all the complexes were modest (i.e. 16–1024 µg mL–1).
The pincer catalysed asymmetric P–H addition of diphenylphosphine to 3-benzylidene-2,4-pentadione is herein reported. Albeit successful in catalysing a series of similar substrates, unexpected chelation of the dione substrate to the palladacycle catalyst resulted in inactivation of the catalyst with adjacent coordination sites. Protected phosphine adducts were isolated and characterised.
Crystal structure determinations show that both RbI and CsI can interact with carboxylate units in a manner consistent with each oxygen atom having a tetrahedral bonding disposition.
CH15693X-Ray Structures and Dynamic Solution Behaviours of Five-Coordinate Nickel(II) Complexes Containing Di- and Tritertiary Arsine Ligands
Nickel(II) complexes containing two tritertiary arsine ligands are found to be five-coordinate in the solid state but undergo a novel fluxionality in solution whereby all six arsine donors contribute to the coordination sphere. Related complexes containing two ditertiary arsine ligands and one or two halides also show that, where a potential sixth donor exists, dynamic solution behaviours operate to utilise it in bonding.
CH15701Self-Assembly of Square-Planar Halide Complexes of Trimethylphosphine-Stabilized Diphenyl-Arsenium, -Stibenium, and -Bismuthenium Hexafluorophosphates
Square-planar halide complexes with four trimethylphosphine-stabilized diphenyl-stibenium or -bismuthenium ions surrounding a central halide ion in discrete centrosymmetrical structures have been prepared. The structures are stabilized by electrostatic interactions between the halide and four stibenium or -bismuthenium cations, as well as four edge-to-face phenyl–phenyl embraces above and below the plane of the main group elements.
CH15697Unique Occurrence of Cationic and Anionic Bis-1,2-diaminocyclohexane Copper(II) Units in a Double Complex Salt
The reaction of (±)-trans-diaminocyclohexane (dach) with copper(ii) sulfate in water resulted in the spontaneous formation of the double complex salt, [Cu(dach)2(H2O)2][Cu(dach)2(SO4)2]·6H2O, which unexpectedly incorporated a Cu(dach)22+ motif in both of its complex cation and anion. Each copper(ii) centre had a trans N4O2-donor coordination shell, yielding an overall Jahn–Teller-distorted octahedral geometry.
A series of thienyl-substituted difluoroboron β-diketonate complexes were prepared to study the effects of conjugation, substituents, and media (CH2Cl2 and polylactide) on optical properties. Red-shifted emission was achieved.
The conformational behaviour of larger calixarenes in the solid state is considered in the context provided by single crystal X-ray studies of p-t-butylcalixarene·2dmso·7H2O and [NMe4][p-t-butylcalixarene-H]·2dmso·H2O.
CH15763Iminoacyl Alkyl Complexes of Zirconium Supported by a Ferrocene-Linked Diphosphinoamide Ligand Scaffold
Ferrocenyldiphosphinoamide-stabilized zirconium alkyl complexes undergo migratory insertion reactions with isocyanides, and in one case, subsequent rearrangement on thermolysis.
The catalytic hydrogenolysis of the sp3–sp2 C–C bond in a trifluoro amide occurs under mild conditions using a phosphine-free catalyst.
CH15795CCC-NHC Pincer Zr Diamido Complexes: Synthesis, Characterisation, and Catalytic Activity in Hydroamination/Cyclisation of Unactivated Amino-Alkenes, -Alkynes, and Allenes
CCC-NHC pincer Zr diamido complexes initiate hydroamination at room temperature. Hydroamination rates are improved using these complexes.
CH15779Experimental and Computational Studies of the Mechanisms of Hydroamination/Cyclisation of Unactivated α,ω-Amino-alkenes with CCC-NHC Pincer Zr Complexes
In the mechanism of the CCC-NHC pincer Zr complex catalysed hydroamination, proton transfer is the turnover limiting step.