Atom transfer radical polymerization.

Metal-catalyzed living radical polymerization.

Controlled/living radical polymerization: Features, developments, and perspectives

Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.

Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives

Functional polymers by atom transfer radical polymerization

Structural and spectral studies of thiosemicarbazones derived from 2-acetylthiophene

Oxidation of [Nb(η5-C5H4But)2(CH2Ph)2] yields the stable cationic benzylidene complex [Nb(η5-C5H4But)2(CHPh)(thf)]BPh4, which readily loses thf to form the C–H activation product [Nb(η5-C4H4But)(η5:η1-C5H4CMe2CH2)(η2–CH2Ph)]BPh4 and reacts with acetonitrile to give the double-insertion product [Nb(η5-C5H4But)2{η2-NC(Me)C(Ph)C(Me)NH}]BPh4.

C–H activation and nitrile insertion reactions of a cationic niobium alkylidene complex

The synthesis and structural characterisation of related novel copper-(I) and -(II) diimine complexes have been described and their application as catalysts for atom transfer polymerisation is noted. The unexpected formation of a methoxy bridged copper(II) diimine complex [{(C10H14N2)CuBr(µ-OMe)}2(MeOH)] 3 from the reaction of a copper(I) diimine complex with phenol is described. Compounds 3 and [{(C10H20N2)CuBr(µ-OMe)}2] 4 appear to be examples of a rare class of alkoxy bridged CuII complexes, with very few similar examples being crystallographically characterised previously.

Copper diimine complexes: the synthesis and crystal structures of [Cu(C10H14N2)2(MeOH)][BF4], [Cu(C10H20N2)2]Br, [{(C10H14N2)CuBr(µ-OMe)}2(MeOH)] and [{(C10H20N2)CuBr(µ-OMe)}2]

New, selective and high-yielding preparations of the mixed-ring complexes [Ti(η5-C5H5)(η5-C9H7)C2] and [Ti(η5-C5H5)(η5-C5H4But)Cl2] are reported. These have been used to prepare a range of mono- and di-substituted titanium(IV) alkyl and benzenethiolate complexes of the form [Ti(η5-C5H5)(η5-ring)(CH2SiMe3)Cl] and [Ti(η5-C5H5)(η5-ring)R2](ring = indenyl or C5H4But; R = Me, CH2Ph, CH2SiMe3 or SPh). While the indenyl ligand in the racemic, chiral-at-metal complex [Ti(η5-C5H5)(η5-C9H7)(CH2SiMe3)Cl] is bound in an η5 fashion, X-ray structural data clearly indicate that there is some ‘η3 ring-slip’ character to the bonding. The NMR and nuclear Overhauser effect experiments conducted on [Ti(η5-C5H5)(η5-C5H4But)(CH2SiMe3)Cl] demonstrate hindered rotation around the Ti–C5H4But bond and show the geometry to be fixed such that the But and SiMe3 groups are remote.

Synthesis and characterisation of (η5-cyclopentadienyl)(η5-ring)titanium alkyl (ring = indenyl or C5H4But) complexes. Crystal and molecular structure of racemic [Ti(η5-C5H5)(η5-C9H7)(CH2SiMe3)Cl]

David J. Duncalf

Papers

Structural and spectral studies of thiosemicarbazones derived from 2-acetylthiophene

C–H activation and nitrile insertion reactions of a cationic niobium alkylidene complex

Copper diimine complexes: the synthesis and crystal structures of [Cu(C10H14N2)2(MeOH)][BF4], [Cu(C10H20N2)2]Br, [{(C10H14N2)CuBr(µ-OMe)}2(MeOH)] and [{(C10H20N2)CuBr(µ-OMe)}2]

Synthesis and characterisation of (η5-cyclopentadienyl)(η5-ring)titanium alkyl (ring = indenyl or C5H4But) complexes. Crystal and molecular structure of racemic [Ti(η5-C5H5)(η5-C9H7)(CH2SiMe3)Cl]

Substituent effects on the cyclo-manganation reaction X-ray crystal structure of Mn{2-(nBu-N=CH) 5-(NO2) C6H3}(CO)4