Magnetic susceptibility of ruthenium(III) in tris-ethylenediamine salts. Effect of outer sphere ligands

The paramagnetic susceptibility of Ru(III) in tris-ethylenediamine salts has been measured as a function of temperature. In all cases the iodide salt exhibits a greater susceptibility than the bromide salt. This difference may be attributed to a larger degree of temperature independent paramagnetism in the iodide complex due to the presence of low lying charge transfer states.     

The chemistry of sulfines. 9. A novel synthesis of α-chloroalkyl alkanethiosulfonate esters

Sulfines react with sulfinyl chlorides giving α-chloroalkyl alkanethiosulfonate esters and with thionyl chloride giving α-chloroalkanesulfenyl chlorides, both in good yields.     

Group IB metal chemistry : V. Some fluxional complexes containing copper or silver

Fluxional poly(pyrazolyl)borate complexes of copper and silver, including the carbonyl Cu(CO)B(pz)₄, contain coordinated and free pyrazolyl groups, which interchange rapidly on the NMR time scale at room temperature; low temperature limiting spectra can be obtained for some copper complexes at ?100°.     

Catalytic hydrogenation of propene over polymer supported rhodium complexes

Hydrogenation of propene and other substrates has been studied in flow and batch reactors using various rhodium catalysts. The results show that in some cases rhodium metal is probably formed, but only if solvent is present. A possible explanation is given.     

Complexes of silver(III) with oxoanions

Silver(III) has a half-life at pH 11 of several hundred seconds in aqueous solutions in the presence of 0.1–1.0 M concentrations of certain basic oxoanions (Oxo) (phosphate, carbonate, borate, pyrophosphate, and arsenate). This compares with a lifetime of a few seconds at pH 11 in the absence of these oxoanions. UV-visible spectra and kinetic data for these solutions are interpreted as evidence for the following equilibria in the pH range 9–13.Ag(OH)₄^?1 + H₂O ? Ag(OH)₃H₂O + OH^? (1)Ag(OH)₄^?1 + Oxo ? Ag(OH)₃Oxo + OH^? (2)Ag(OH)₃Oxo + H₂O ? Ag(OH)₂(Oxo)H₂O + OH^? (3) Values of K₃ lie in the range 10^?3 < K₃ <10⁴ M for the systems studied. K₂ is estimated to be ～10² for phosphate and slightly smaller for the other systems. Ag(OH)₄^? undergoes an unusual reaction with pyrophosphate at pH ～ 8 to form a novel silver(II) complex, [Ag(P₂O₇)₂]^6?, for which EPR and electronic absorption spectral parameters are reported.     

Silicon in synthesis: The use of trimethylsilyl cyanide for the synthesis of aliphatic cyanomethylethers

The conversion of aliphatic alcohols into cyanomethyl ethers $\text{via}$ treatment of methyl sulfoxymethyl ethers with trimethylsilyl cyanide - zinc iodide is described.     

Studies on terpenes—7: A Short route to a pentalenolactone e precursor

The bicyclic enone 6 was converted into the adduct 13 by photochemical addition of aliene, and then elaborated through a fragmentation sequence into the -methylene ketone 17.     

Silicon in synthesis: 1-trimethylsilyl-1-methoxy allene; a reagent for the direct conversion of aliphatic aldehydes into 2-trimethylsilyl furans

3-Lithio 1-trimethylsilyl-1-methoxy allene $\text{4}$ reacts with aldehydes to give adducts that are readily transformed into 2-trimethylsilyl furans.     

Crystal structure of dimeric p-phenoxyphenyltellurium(IV) trichloride

p-PhOC₆H₄TeCl₃ crystallises with a dimeric molecular unit. The two approximately square pyramidal coordination polyhedra are linked trans to each other through two bridging chlorine atoms. The dimeric units are further connected through Te…Cl secondary interactions producing a distorted octahedral geometry about each tellurium atom. The crystals are triclinic, space group P$\text{1}$, with unit cell dimensions a 8.521(2), b 10.917(2), c 14.813(2) Å, α 81.84(1), β 83.38(1), γ 88.41(1)°, V 1353.4(4) ų and Z = 2(dimers) from 3887 observed reflections [I > 3σ(I)], R = 0.0359.     

Macroexpansion methodology : Medium ring synthesis based on an eight unit ring expansion process

Treatment of 1,2-(E,E)-di(1-buta-1,3-dienyl)cyclohexanol (21) with potassium hydride in tetrahydrofuran at room temperature resulted in the facile formation of a 14-membered ring dienolate which on kinetic protonation provided cyclotetradeca-3,5,7-trien-1-one. This novel rearrangement which provides the basis for an efficient, eight unit ring expansion method was also observed when 5,8-dimethyl-5-hydroxy-1,3,7,9-decapentaene (28), the acyclic analogue of 21, was treated with potassium hydride in tetrahydrofuran. Methodology for the preparation of 21 and 28 including the preparation of 1-lithio-1,3-butadiene is also described.     

The preparation of di- and tri-phenylstannyl esters of aromatic dithio acids,and some of their reactions

Some crystalline di- and tri-phenylstannyl esters [ArCS₂SnPh₃ and (ArCS₂)₂SnPh₂] of aromatic dithio acids have been prepared in good yields and characterized. Preferential cleavage of the SnS bond of the ester was observed by treating them with primary and secondary amines as well as with phenacylidenetetramethylenesulfurane.     

Cyclometallation reactions XII. On the effect of various leaving groups on internal metallation reactions with alkylmanganese complexes

The interaction of azobenzene and MnR(CO)₅ (R  Me, Et, CH₂Ph, CH₂-C₆Me₅, COCF₃, COCH₂C₆F₅, COCH₂OPh, Ph or C₆F₅) affords M$\text{n(C}{}_6\text{H}{}_4\text{NN}$Ph)-(CO)₄, together with a binuclear complex Mn₂(CO)₆(C₁₂H₁₀N₂) in some cases. The metallation reaction is shown to proceed most readily with Mn-(CH₂Ph)(CO)₅; with this reagent, the metallated complexes M$\text{n(C}{}_6\text{H}{}_4\text{CH}{}_2\text{P}$Me₂)-(CO)₃[PMe₂(CH₂Ph)] (two isomers) and M$\text{n(C}{}_6\text{H}{}_4\text{CH}{}_2\text{A}$sMe₂(CO)₄ have been obtained on treatment with EMe₂(CH₂Ph) (E  P and As, respectively).     

Synthesis of homoharringtonine and its derivative by partial esterification of cephalotaxine.

Homoharringtonine $\text{2}$ and dehydrodesoxy homoharringtonine $\text{4}$ were synthesized by partial esterification of cephalotaxine.     

Reaction of perfluoroalkylethylens with nucleophiles

Perfluoroalkylethylenes react with some carbon-, oxygen-, sulfur-, selenium-, nitrogen-, and phosphorus-based nucleophiles by formal S_N2′ displacement of fluoride ion.