Synthesis,reactions and catalytic activity of some mixed trifluorophosphine(triphenylphosphine)hydrido complexes of cobalt(I)

The complexes CoH(PF₃)_4?n (PPh₃)_n (n = 1–3) have been prepared by low from the reaction between CoH(PF₃)(PPh₃)₃ and butadiene. The hydrido complexes are active catalysts for the isomerisation of 1-octene to 2-octene under hydrogen or nitrogen.     

Metal to ligand group transfer reactions : II. Reactions of some π-allylrhodium(I) complexes with trifluoroacetic acid and alkyl,acyl and trimethyltin halides

Rh(π-C₃H₅)(PF₃)₃ (I), reacts with trifluoroacetic acid to form propene and [Rh(CF₃COO)(PF₃)₂]₂ (II). I reacts with t-butyl bromide to give [RhBr(PF₃)₂]₂ and a mixture of propene and 2-methyl-1-propene and with n-propyl bromide to give propene and [RhBr(PF₃)₂]₂. Rh(π-C₃H₅)(PPh₃)₂ (III), and t-butyl bromide yield propene and 2-methyl-1-propene. In these reactions a mechanism involving β-hydrogen abstraction and hydrogen migration via the metal to carbon is proposed. When III reacts with Me₃SnCl the Me₃Sn—moiety migrates intact to the π-allyl group. I reacts with acetyl chloride to give propene, [RhCl(PF₃)₂]₂ and the carbonyl rhodium complex Rh₂Cl₂(PF₃)₃(CO). II does not apparently undergo phosphine ligand exchange unlike the analogous halogeno-bridged dimers.     

Perfluorinated polymer surfaces comprising SF5-terminated long-chain perfluoroacrylate

A new perfluorinated acrylate monomer containing the SF₅(CF₂)₆-perfluorinated side chain was synthesized and polymerized into films. Bulk monomer characterization is consistent with the molecular structure based on FTIR, mass spectrometry and NMR analyses. The surface properties of polymer coatings were studied with aqueous wetting (contact angle) and X-ray photoelectron spectroscopy (XPS) methods. The surface composition is shown to be highly enriched in the terminal side chain SF₅-chemistry and exhibits properties consistent with a highly apolar, non-wetting perfluorinated polymer surface. Depth-dependent XPS studies using angular-resolved methods (ADXPS) confirmed a non-stoichiometric enrichment of sulfur and fluorine at the film ambient interface, consistent with a surface presence of the terminal SF₅-group and possibly film structural anisotropy in the surface zone. Time-of-flight (TOF) secondary ion mass spectrometry (SIMS) analysis supplements the XPS data by showing the presence of all expected SF₅-acrylate chemistry components in the outer 15 Å of the film surface.     

Regioselective supramolecular catalysis. Exploiting multiple binding motifs in propanediurea molecular clips

Molecular clips derived from 2,4,6,8-tetraazabicyclo[3.3.1]nonane-3,7-dione promote increased regioselectivity in the SO₂Cl₂-mediated electrophilic aromatic chlorination of ortho-cresol leading to para/ortho ratios (R_p/o) <25; approximately six times larger than in the absence of the clip. Specific recognition events involving hydrogen-bond, π-π and dative covalent interactions are implicated.     

Hexaphosphapentaprismane: a new gateway to organophosphorus cage compound chemistry

Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light-induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis-[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single-crystal X-ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13.