Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
Australian Journal of Chemistry

Australian Journal of Chemistry

Volume 65 Number 7 2012

RESEARCH FRONT: Dedication to Allan White

CH12190The Chemistry of Transition Metal Ethyne-1,2-diyl Complexes

Christopher S. Griffith and George A. Koutsantonis
pp. 698-722
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The chemistry and reactivity of ethyne-1,2-diyl compounds, LnM–CC–MLn, is reviewed. These complexes are simple analogues of organic alkynes, or dimetalloalkynes. Reactivity patterns mimic those of simple organic alkynes but have reactive M–C(sp) bonds that sometimes participate in the formation of multimetallic compounds with metal electrophiles.

CH11338 Reactions of Aniline with Copper(II) Compounds in Relation to the Formation of Copper-Polyaniline Composites

Adeline Le Cocq, Marija R. Gizdavic-Nikolaidis, Allan J. Easteal and Graham A. Bowmaker
pp. 723-729
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Reactions of aniline with a copper(ii) sulfate, chloride, or bromide in aqueous solution, yield copper(ii)-aniline complexes, in contrast to previously reported studies, which claimed the formation of copper-polyaniline composites.

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Rubidium and caesium orthanilates form chemically stable two-dimensional layered coordination polymeric structures based on stereochemically variable metal centres: six-, seven-, eight- and ten-coordinate in the rubidium complex and seven-coordinate in the caesium complex, these compounds representing rare examples of structurally characterized metal complexes with orthanilic acid.

CH11449 Axially Aligned Confinement of 1,4-Bis(triethylammoniomethyl)benzene by Two p-Sulfonatocalix[4]arenes

Irene Ling, Yatimah Alias, Munirah Sufiyah Abdul Rahim, Brian W. Skelton, Lindsay T. Byrne and Colin L. Raston
pp. 755-762
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A multi-component bi-layer complex involving 1,4-bis(triethylammoniomethyl)benzene cation, p-sulfonatocalix[4]arene anion and phosphonium cation shows the preferential binding of the bis-triethylammonium cation in the cavity of two geometrically opposed calixarenes with the same molecular capsules persisting in solution.

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Organometallics with various donor–bridge–acceptor arrangements allow investigation of the key factors affecting the properties of these multifunctional molecular systems. Herein, reactions of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with Fe(C≡CR)(dppe)Cp* and Ru(C≡CR)(PPh3)2Cp (R = H, Ph) are described. Formed are the mono-cation (by oxidation in the iron series), zwitterionic complexes, and complexes formed by regioselective [2 + 2]-cycloaddition and subsequent ring-opening reactions; elimination of HCN (in the ruthenium series) was also observed.

CH11510 Triosmium Clusters Containing 2-Mercaptobenzothiazolate Ligands

Md. Abdul Khaleque, Kazi A. Azam, Md. Manzurul Karim, Shishir Ghosh, Graeme Hogarth and Shariff E. Kabir
pp. 773-778
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Reaction of the labile cluster [Os3(CO)10(NCMe)2] with 2,2′-benzothiazyl disulfide has been studied. Three new triosmium clusters have been synthesized and structurally characterized from this study.

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An X-ray crystallographic study using two different radiation wavelengths was performed on 7-diethylamino-[1',3′,3′-trimethyl-4-((1,3,3-trimethyl-1,3-dihydro-2H-indole-2-ylidene)methyl)-1',3,3′,4-tetrahydrospiro[chromene-2,2'-indole]] crystals obtained from the condensation of two molecules of Fischer’s base with 4-(dimethylamino)salicylaldehyde. No significant deviations between the final models were observed.

CH11468The Nature of Hydrogen Bonding Involving the Siloxane Group

Simon Grabowsky, Jens Beckmann and Peter Luger
pp. 785-795
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Geometry, electron density, and electron localizability properties are used to clarify the nature of unusual hydrogen bonding to the siloxane linkage in a computational study. It is described how the basicity of the siloxane linkage can be significantly increased through variation of the Si–O–Si bond angle and how this is reflected in corresponding indicators of hydrogen bonding.

CH12069Lanthanoid and Alkaline Earth Complexes Involving New Substituted Pyrazolates

Glen B. Deacon, Peter C. Junk and Aron Urbatsch
pp. 802-810
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A range of alkaline earth and lanthanoid complexes involving new substituted pyrazolates of the type [M(pz)x(solv)y] were prepared. They were structurally and spectroscopically characterized. Also, the first transoid lanthanoid iodo pyrazolate complex, [LnII(pz)I(thf)4], was isolated.

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The 2 : 1 tetrahedral complexes of the bidentate diphosphine ligands cis-bis(diphenylphosphino)ethene (dppey), cis-bis(diphenylphosphino)ethane (dppe), and cis-bis(diphenylphosphino)propane (dppp) with copper(i), silver(i), and gold(i) have been synthesized as tetraphenylborate salts and characterized by NMR spectroscopy, electrospray mass spectrometry, and single crystal X-ray structure determinations at 200 K.

CH12044Synthesis, Solid-state Structures, Solution Behaviour and Catalysis Studies of Nickel Complexes of Bis(benzimidazolin-2-ylidene)pyridine Pincer Ligands

Karen D. M. MaGee, Guy Travers, Brian W. Skelton, Massimilliano Massi, Alan D. Payne and David H. Brown
pp. 823-833
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The solution behaviour of nickel complexes of bis(benzimidazolin-2-ylidene)pyridine pincer ligands suggests an equilibrium between four- and five-coordinate complexes.

CH12054 Organometallic Complexes for Non-Linear Optics. 51. Second- and Third-Order Non-Linear Optical Properties of Alkynylgold Complexes

Adam Barlow, Bandar Babgi, Marek Samoc, T. Christopher Corkery, Stijn van Cleuvenbergen, Inge Asselberghs, Koen Clays, Marie P. Cifuentes and Mark G. Humphrey
pp. 834-841
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Quadratic optical non-linearities of gold alkynyl complexes increase on π-system lengthening and on introduction of electron-releasing substituents on the π-bridge ring adjacent to the metal centre, while maximal values of the effective two-photon absorption cross-sections of 1,4-{(PCy3)Au(C≡C)}2C6H4 and {(PCy3)Au(C≡C-4-C6H4C≡C)}6C6 increase non-linearly on proceeding from linear complex to 6-fold-symmetric complex.

CH12045Synthesis and Coordination Chemistry of 2-(Di-2-pyridylamino)pyrimidine; Structural Aspects of Spin Crossover in an FeII Complex

Rachel S. Crees, Boujemma Moubaraki, Keith S. Murray and Christopher J. Sumby
pp. 842-850
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2-(Di-2-pyridylamino)pyrimidine forms mononuclear trans-[Fe(NCS)2(L)2], [Cu(L)2(H2O)](BF4)2·H2O and [PdCl2(L)] complexes, a dinuclear [(PdCl2)2(L)]·¾H2O complex, and a discrete [Ag2(L)4](PF6)2 metallomacrocycle. trans-[Fe(NCS)2(L)2] undergoes a temperature-dependent spin crossover, which was examined by magnetic and structural measurements.

CH12058Copper(II) and Palladium(II) Complexes with Cytotoxic and Antibacterial Activity

Anwen M. Krause-Heuer, Peter Leverett, Albert Bolhuis and Janice R. Aldrich-Wright
pp. 860-873
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Eight square pyramidal copper complexes and four square planar palladium complexes with general structure [Cu(IL)(AL)H2O]2+, were synthesised. The crystal structures of [Cu-PHENSS](ClO4)2·H2O and [Cu-56MESS](ClO4)2·1.5H2O are reported. The copper complexes display some anticancer and antibacterial activity. The palladium complexes all have IC50 values of ~10 μM in the L1210 cell line and minimal antibacterial activity.

CH12052Iron(II) Mononuclear Materials Containing Functionalised Dipyridylamino-Substituted Triazine Ligands: Structure, Magnetism and Spin Crossover

Hayley S. Scott, Tamsyn M. Ross, Stuart R. Batten, Ian A. Gass, Boujemaa Moubaraki, Suzanne M. Neville and Keith S. Murray
pp. 874-882
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Members of a family of iron(II) complexes of a dipyridylamino-substituted triazine ligand (DTAC) of formula [Fe(DTAC)2(anion)2], display high-spin structural and magnetic features when anion = NCS and NCSe and spin-crossover behaviour when anion = N(CN)2 and NCBH3.

CH12042Bismuth(III) Thiobenzoates and their Activity against Helicobacter pylori

Philip C. Andrews, Richard L. Ferrero, Peter C. Junk, Jonathan G. Maclellan and Roshani M. Peiris
pp. 883-891
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Six homo- and heteroleptic bismuth(iii) thiobenzoates of form Ph3-nBiLn (n = –3) have been synthesised by solvent-mediated and solvent-free methods. The structures of the compounds derived from thiobenzoic acid have been determined by X-ray crystallography. Bactericidal studies against three strains of Helicobacter pylori show a minimum inhibitory concentration of 6.25 µg mL–1 for all compounds, indicating that the high activity is independent of ligand type and degree of substitution at the Bi(iii) centre.

CH12032Weathered Ilmenite: Diverse Mechanisms of Sintering and Association with Contaminants

Terry C. Parks, Bob van Emden, Nathan A. S. Webster, Richard R. Merritt, Jim Graham and Frank J. Lincoln
pp. 892-904
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Extreme weathering breaks ilmenite, FeTiO3, into separate, surface-active oxyhydroxides that are prone to gather undesirable contaminants. However, in reduction kilns the most influential ‘contaminant’ may be water, which promotes reactivity and causes ilmenite grains to expand, sometimes to cenospheres. In complex ways, such ilmenite accumulates in unusable sinter.

CH12100Linear Trinuclear Copper(II) Complexes Derived from the Nucleophilic Addition Products of Dicyanonitrosomethanide [C(CN)2(NO)]: Syntheses, Structures, and Magnetic Properties

Mohd. R. Razali, Aron Urbatsch, Stuart K. Langley, Jonathan G. MacLellan, Glen B. Deacon, Boujemaa Moubaraki, Keith. S. Murray and Stuart R. Batten
pp. 918-925
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Two novel trinuclear CuII complexes have been synthesised from the nucleophilic addition derivatives of the small nitrile anion, dicyanonitrosomethanide (dcnm).

CH12145Copper(II) Complexes of Two New Pyridyl–Aliphatic Amine Ligands: Synthetic, Structural, EPR, and Magnetic Studies

Young Hoon Lee, Hari Kristopo, Arim Woo, Mi Seon Won, Shinya Hayami, Pierre Thuéry, Ok-Sang Jung, Hong In Lee, Bok Jo Kim, Leonard F. Lindoy and Yang Kim
pp. 926-930
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Two new polyamine ligands, L1 and L2, incorporating pyridyl and aliphatic amine donor sites yield the mono- and binuclear complexes [Cu(L1)](ClO4)2 (1) and [Cl2Cu(L2)CuCl(H2O)]ClO4 (2), respectively, in which the copper ions each exhibit distorted square pyramidal coordination; in binuclear 2 non-equivalent coordination behaviour is present at the individual copper sites.

CH12161Synthesis of Poly(2-Hydroxyethyl Methacrylate) Sponges via Activators Regenerated by Electron-transfer Atom-transfer Radical Polymerization

Stefan M. Paterson, David H. Brown, Jeremy A. Shaw, Traian V. Chirila and Murray V. Baker
pp. 931-934
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This communication describes the use of activators regenerated by electron-transfer atom-transfer radical polymerization to synthesize poly(2-hydroxyethyl methacrylate) sponges.

CH12183Novel Semiconducting Biomaterials Derived from a Proline Ester and Tetracyanoquinodimethane Identified by Handpicked Selection of Individual Crystals

Lisandra L. Martin, Jinzhen Lu, Ayman Nafady, Thanh Hai Le, Amal I. Siriwardana, Xiaohu Qu, Daouda A. K. Traore, Matthew Wilce and Alan M. Bond
pp. 935-941
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The reaction of N,N-dimethyl-d-proline-dimethylester (Pro(CH3)3+) with LiTCNQ (TCNQ = tetracyanoquinodimethane) in water resulted in a mixture of crystals, 1 : 1 [Pro(CH3)3TCNQ] and 2 : 3 ([(Pro(CH3)3)2(TCNQ)3]). Each crystal is analysed by X-ray, infrared, Raman and electrochemistry. The electrochemical method provides an exceptionally sensitive method of distinguishing differences in stoichiometry.

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Professor Kenneth Seddon OBE, one of AJC’s longest-standing Editors, sadly passed away on 21 January from prostate cancer. Ken was one of the world's best ionic liquids experts. His consistent unwavering support, loyalty and advocacy for AJC over the last 10 years will be sorely missed.