Silica-supported tantalum hydride activates at low temperature the C–H and the C–D bonds of cyclooctane and CD4, respectively, to form the corresponding cyclooctyl and perdeuteriomethyl-tantalum surface complexes; these complexes are transformed under molecular oxygen into the corresponding tantalum-alkoxy derivatives which with acetic acid give rise to the corresponding alkylacetates.
The novel molecular conductors, (DIETS)4M(CN)4(M = Ni, Pd, Pt) where reticulated donor-anion contacts are constructed using the strong and directional –-I ⋯ NC– interaction, are synthesized and characterized.
Hydrofluorination of unsaturated compounds proceeds by reaction with solid potassium hydrogen fluoride and silicon tetrafluoride to afford the corresponding fluorides in high yields.
For each boronic acid group in 1 one hydrogen atom makes a hydrogen bond to an alkyne carbon atom as well as an intermolecular O–H ⋯ O bond; structural effects indicate the boronic acid group to be σ-electron releasing and π-electron withdrawing.
Molecular mechanics modelling demonstrates the geometric and energetic viabilities of proposed novel nucleotide bases in Hoogsteen interactions confined to natural DNA triplet configuration.
In radio frequency (RF) sustained plasmas of propenoic ('acrylic') acid, trimeric cations are detected by MS, and their concentration correlates with retention of acid functionality in the polymer product.
A novel 30-membered macrocycle containing four endocylic, neutral pyrazole groups, binds two Cu-II ions, where a flexible propylene spacer separates the Cu-II ions by 7.14 Angstrom; the crystals structure of the mixed-anion complex[CU2(L)Cl-2(EtOH)(2)](NO3)2 shows that each Cu-II ion is bound in a square-pyramidal N(4)X chromophore.
Alkoxy-substituted biphenyls are highly polarized in S-1, with the negative charge residing on the ring not possessing the alkoxy group, enabling the photogeneration of spectrophotometrically observable transient biphenyl quinone methides by laser flash photolysis.
[Vanadium(salen)benzilate].1.5CH(2)Cl(2), the preparation, X-ray structure, redox and spectroscopic properties of which are reported, is the first monomeric nan-ore vanadium(iv) complex with concomitant vicinal carboxylate and hydroxylate coordination.
In CH2Cl2 solution the phosphinate anion BrCH2CH2(CH2)(n)CH2(Ph)P(OO- cyclises only 4.3 times faster when n = 0 (five-membered ring product) than when n = 1; for the thiophosphinate anion ClCH2CH2(CH2)(n)CH2(Ph)P(SO- cyclisation (via sulfur) is still only 30 times faster when n = 0 than when n = 1.
The mechanism of titanocenedichloride-catalysed hydromagnesiation reaction of alkynes with an alkyl Grignard reagent is elucidated and it is revealed that the regiochemistry of the, reaction controlled at the step of transmetallation from titanium to magnesium.
For the first time, reversible electrochemical:insertion of unsolvated lithium into graphite previously treated in LiClO4-ethylene carbonate solution is carried out in a LiClO4-propylene carbonate electrolyte.
Thermolysis of benzocyclobutenone in dichlorobenzene in the presence of [60]fullerene affords the o-phenylene(methylene)ketene-C-60[4+2] cycloadduct, while similar thermolysis of benzocyclobutenedione gives no cycloadduct; irradiation of the dione with [60]fullerne, produces a phthalide-1-ylidene-C-60 adduct.
Photochemical and thermal reactions of an endohedral metallofullerene Gd@C-82 with disilirane afford an exohedral adduct.
The title ligand [L(1)]- forms 2:1 complexes [M(III)(L(1))2]+(M = Sm, U) in which the metal ions are in an icosahedral N-12 coordination environment from the two interleaved hexadentate ligands.
The complex [(bpy)(2)Ru(tpphz)](2+) (tpphz = tetrapyridophenazine), is obtained by reaction of [(bpy)(2)Ru(phendione)](2+) with 5,6-diamino-1,10-phenanthroline; upon reaction with [(bpy)(2)Ru(Me(2)C0)(2)](2+), the fully conjugated dimer[(bpy)(2)Ru(tpphz)Ru(bpy)(2)](4+) is obtained.
The palladium catalysed cyclisation of aryl iodides onto proximal allenes occurs at the centre carbon atom of the allene forming a five- or six-membered rings and generating a pi-allyl intermediate. The regiochemistry of attack of secondary amines on the pi-allyl intermediate is sensitive to added inorganic base, steric effects and the nature of the adjacent heteroatom.
The zinc hydroxide complex {[Pim(Pri,But)]ZnOH}(ClO4) is synthesized by the reaction of [Pim(Pri,But)] with Zn(ClO4)(2) . 6H(2)O; {[Pim(Pri,But)]ZnOH}(ClO4) is the first structurally characterized monomeric zinc hydroxide complex supported by imidazole functionalities and is therefore an excellent structural model for the active site of carbonic anhydrase.
Stable functionalised gold nanoparticles are prepared by simultaneous reduction of tetrachloroaurate ions and attachment of bifunctional organic thiol molecules to the growing gold nuclei leading to a material whose chemical behaviour is characterised by the vacant functionality of the bifunctional thiol ligand.
Oxygen dimers on the (2 x 1) reconstructed surface of Na0.65WO3(001) have been observed by scanning tunnelling microscopy, with an O-O separation (2.2 Angstrom) that is significantly less than twice the ionic radius of the oxide ion (2.8 Angstrom).
