Reactions of methyltris(triarylphosphine)cobalt : I. Formation of biaryls

Methyltris(triarylphosphine)cobalt (Ar₃P)₃CoCH₃, decomposes in solutions of THF, benzene or chlorobenzene to yield biaryls. Coupling to biaryls occurs at the ring carbon originally bonded to phosphorus. Mixed biaryls are obtained from crossover reactions of complexes bearing different triarylphosphine ligands and reactions of complexes with free triarylphosphines.     

Fragmentation of 1-aryl-5-(2-dialkylaminovinyl)-1H-tetrazoles upon electron impact

The mass spectrometric behaviour of 1-aryl-5-(2-dialkylaminovinyI)-lH-tetrazoles was studied, especially 1-phenyl-5-(2-dimethylaminovinyl)-l H-tetrazole as a typical example of D- and ¹⁵N-labelled derivatives revealed a rearrangement via a carbodiimide-like intermediate ion.     

Alkylation of ethylenethiourea with alcohols: a convenient synthesis of S-alkyl-isothioureas without toxic alkylating agents

The alkylation of ethylenethiourea with alcohols and aqueous acids (HCl, HBr, and HI) allows the synthesis of the respective S-alkyl-isothioureas in high yield and purity. Consistently high yields (91-98%) were obtained with 56% HI, the yields for 48% HBr (48-93%) and 37% HCl (36-85%) were lower and varied with the type of alcohol. The method is a convenient low-cost alternative to the use of alkyl iodides and an easy access to the S-tert-butyl isothiourea.     

Electron transfer initiated Diels-Alder reaction with allenes as dienophiles

The first examples of using aryl allenes as dienophiles in the electron transfer induced Diels-Alder reaction are described. According to mechanistic tests the reaction proceeds via a cycloaddition of the diene^+· to the allene.     

Double-layer effects on simple electrode reactions III. The reduction of Eu3+ and Cr3+ in the presence of thiocyanate anions. Evidence for ligand bridging

The rates of reduction of Eu³⁺ and Cr³⁺ have been measured in mixed perchlorate + thiocyanate electrolytes at constant ionic strength, using low concentrations of thiocyanate to minimize its association with the cationic reactants. The effect of adsorbed thiocyanate anions on the reduction kinetics of Cr³⁺ resembled those produced by iodide and bromide on both Cr³⁺ and Eu³⁺. However, thiocyanate exhibited an unusual catalytic effect on the reduction of Eu³⁺ which was identified as arising from a reaction pathway involving thiocyanate-bridging between the mercury surface and the Eu³⁺. The diagnostic criteria used to support the proposed mechanism included analysis of the rate—potential behavior and of the effects of competitively adsorbed iodide ions upon the reduction rates.     

Metallacycloalkanes: I. Preparation and characterisation of α,α′-bipyridyl-5-nickela-3,3,7,7-tetramethyl-trans-tricyclo[4.1.0.02,4]heptane

Oxidative addition of 2 molecules of 3,3-dimethylcyclopropene (I) to α,α′-bipyridyl(1,5-cyclooctadiene)nickel(0) (III) gave the title compound (IV) in over 90% yield. Complex IV was characterized by mass, ¹H NMR and ¹³C NMR spectroscopy. Its structure was determined by X-ray diffraction (a 13.7081(2), b 14.638(2), c 9.5139(1) Å, β 110.82(1)°, C2/c, R = 0.05 for 1614 reflections).     

Bistable ferroelectric liquid crystal photoswitch triggered by a dithienylethene dopant

The spontaneous polarization (PS) of a ferroelectric liquid crystal is modulated reversibly by photocyclization of the dopant 1,2-bis[5'-(4' '-heptyloxyphenyl)-2'-methylthien-3'-yl]perfluorocyclopentene. The magnitude of PS photomodulation increases with dopant concentration up to 3 mol %, and the resulting photoswitch is fatigue resistant and bistable. To the best of our knowledge, this is the first example of a bistable ferroelectric liquid crystal photoswitch to be reported in the literature.     

Molecular potential-energy surfaces for chemical reaction dynamics

This paper reviews the construction of molecular potential-energy surfaces by an interpolation method which has been developed over the last several years. The method uses ab initio quantum chemistry calculations of the molecular electronic energy in an automated procedure to construct global potential- energy surfaces which can be used to simulate chemical reactions with either classical or quantum dynamics. The methodology is explained and several applications are presented to illustrate the approach. Received: 22 February 2002 / Accepted: 2 May 2002 / Published online: 6 November 2002 Correspondence to: M. A. Collins e-mail: collins@rsc.anu.edu.au Acknowledgements. The methods described in this overview are the result of collaborations with former members of my group, in particular with Josef Ischtwan, Meredith Jordon, Keiran Thompson and Ryan Bettens. I am also indebted for inspiration gained from many discussions with my colleagues Leo Radom and Donghui Zhang (National University of Singapore). This work has been supported by the Supercomputer Facility of the Australian National University and the Australian Partnership for Advanced Computing.     

Polystyrene resins with immobilized polyamines: Preparation,characterization, and ability to bind Cu(II) ions

Three polyamine ligands, ethylenediamine (EDA), diethylenetriamine (DTA), and triethylenetetramine (TETA), were bound to three chloromethylated “popcorn” polystyrene resins (16, 50, and 100% phenyl ring substitution) with the use of pyridine as the reaction medium. The rate of chloride displacement decreased with increasing molecular weight of the amine and higher degree of resin chloromethylation, while the extent of multiple attachments to the polymer matrix increased. The additional crosslinking, a result of multiple attachments, caused the polyamine resins to swell to a lesser extent in pyridine and water. The ability of the insoluble polyamine–polystyrene resins to chelate Cu²⁺ ions from dilute solutions (200 ppm) was determined at pH 5. With EDA resins the capacity for Cu²⁺ increased with increasing amount of the bound polyamine, with DTA it remained unchanged, while with TETA it was found to decrease.