Synthesis and structure of an aminoethyl-functionalized cyclopentadienyl vanadium(I) dinitrogen complex.

Reduction of a V(III) complex [(eta(5),eta(1)-C(5)H(4)CH(2)CH(2)NMe(2))VCl(2)(PMe(3))] in the presence of diphenylacetylene under nitrogen atmosphere yields a novel V(I) dinitrogen-bridged complex {[eta(5)-(C(5)H(4)CH(2)CH(2)NMe(2))]V(PhC[triple bond]CPh)(PMe(3))}(2)(mu-N(2)).

An efficient yttrium catalysed version of the "Aufbaureaktion" for the synthesis of terminal functionalised polyethylene.

The cationic lanthanoid alkyl complexes (NCN)YR(THF)(+) (R = CH(2)SiMe(3)) bearing a NCN-ligand based on N,N'-bis(2,6-diisopropylphenyl)-benzamidine (AmH), N-[6-(2,4,6-triisopropyl-phenyl)-pyridin-2-yl]-(2,6-diisopropyl)aniline (ApH) or 1,3-bis(2,6-diisopropylphenyl)-2,2-dimethylguanidine (GuaH) combined with an excess of trialkyl aluminium compounds (AlR(3); R = Et, iso-Bu, n-Oct) are efficient catalysts for the highly controlled coordinative chain transfer polymerisation (CCTP) of ethylene, a catalysed version of the "Aufbaureaktion". The aluminium terminated polyethylene (PE) can be oxidised to yield long chain alcohols which are the basis for a diverse polymer chemistry.

Amine catalyzed solvent C-H bond activation as deactivation route for cationic decamethylzirconocene olefin polymerization catalysts.

The C-D activation of bromobenzene-d(5) by [Cp*(2)ZrMe(BrC(6)D(5)-kappaBr)][B(C(6)F(5))(4)] to form sigma-aryl complex [Cp*(2)Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)] is accelerated when the decamethylzirconocene methyl cation is generated in the presence of tertiary amines. Computational studies suggest that the overall sigma-bond metathesis reaction proceeds, in the presence of tertiary amines, via initial deprotonation of bromobenzene in the coordination sphere of the metal center. In a subsequent step, the resulting neutral methyl aryl species, Cp*(2)ZrMe(2-BrC(6)D(4)), reacts with the concurrently generated trialkylammonium cation to generate [Cp*(2)Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)].

Versatile coordination of cyclopentadienyl-arene ligands and its role in titanium-catalyzed ethylene trimerization.

Cationic titanium(IV) complexes with ansa-(eta(5)-cyclopentadienyl,eta(6)-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C(1) bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the eta(6)-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(N(i)Pr(2))(NC(6)H(4)-4-Me)(+) feature eta(1)-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

A [4Fe-4S] cluster dimer bridged by bis(2,2':6',2''-terpyridine-4'-thiolato)iron(II).

The use of 2,2':6',2''-terpyridine-4'-thiol (tpySH) was explored as a bridging ligand for the formation of stable assemblies containing both [4Fe-4S] clusters and single metal ions. Reaction of tpySH (2 equiv) with (NH4)2Fe(SO4)(2).6H2O generated the homoleptic complex [Fe(tpySH)2](2+), which was isolated as its PF6(-) salt. The compound could be fully deprotonated to yield neutral [Fe(tpyS)2], and the absorption spectrum is highly dependent on the protonation state. Reaction of [Fe(tpySH)2](PF6)2 with the new 3:1 site-differentiated cluster (n-Bu4N)2[Fe4S4(TriS)(SEt)] yielded the first metal-bridged [4Fe-4S] cluster dimer, (n-Bu4N)2[{Fe4S4(TriS)(mu-Stpy)}2Fe]. Electrochemical studies indicate that the [4Fe-4S] clusters in the dimer act as independent redox units, while UV-vis spectroscopy provides strong evidence for a thioquinonoid electron distribution in the bridging tpyS(-) ligand. TpySH thus acts as a directional bridging ligand between [4Fe-4S] clusters and single metal ions, thereby opening the way to the synthesis of larger, more complex assemblies.

Enantioselective palladium-catalysed conjugate addition of arylsiloxanes.

The complex formed from Pd(CH(3)CN)(4)(BF(4))(2) and (R,R)-MeDUPHOS is a highly enantioselective catalyst for the asymmetric conjugate addition of aryltriethylsiloxanes to a variety of unsaturated ketones, lactones and lactams.

Selective co-aggregation of gold nanoparticles functionalised with complementary hydrogen-bonding groups.

Molecular recognition between two species of Au55 clusters bearing complementary hydrogen-bonding groups provides a facile route to accomplish solution-based assembly of two-component nanoparticle aggregates.

Synthesis and reactivity of mono(amidinate) organoiron(II) complexes.

The mono(amidinate) iron(ii) ferrate complex [{PhC(NAr)(2)}FeCl(micro-Cl)Li(THF)(3)] (1, Ar = 2,6-iPr(2)C(6)H(3)) was prepared and was found to undergo ligand redistribution in non-coordinating solvents to give the homoleptic [{PhC(NAr)(2)}(2)Fe] (2) as the only isolable product. Reaction of with alkylating agents also induces this redistribution, but the presence of pyridine allows isolation of the four-coordinate 14 VE monoalkyl complex [{PhC(NAr)(2)}FeCH(2)SiMe(3)(py)] (4). Generation of the 12 VE alkyl via pyridine abstraction from 4 by B(C(6)F(5))(3) again induced ligand redistribution. Attempts to trap a 12 VE alkyl species with CO led to the isolation of a dimeric Fe(0)-Li-ferrate complex (3) with a carbamoyl ligand, derived from CO insertion into the iron-amidinate bond.

Reversible chain transfer between organoyttrium cations and aluminum: synthesis of aluminum-terminated polyethylene with extremely narrow molecular-weight distribution.

Aminopyridinato-ligand-stabilized organoyttrium cations are accessible in very good yield through alkane elimination from trialkyl yttrium complexes with sterically demanding aminopyridines, followed by abstraction of one of the two alkyl functions using ammonium borates. At 80 degrees C and in the presence of small amounts of aluminum alkyl compounds, very high ethylene polymerization activities are observed if very bulky aminopyridinato ligands are used. During these polymerizations a reversible polyethylene chain transfer is observed between the organoyttrium cations and aluminum alkyls. The chain-transfer catalyst system described here is able to produce relatively long-chain (up to 4000 g mol-1) Al-terminated polyethylene with a molecular-weight distribution<1.1. In the synthesis of higher molecular PE a slight increase in polydispersity with increasing chain length (15,600 g mol-1, approximately 1.4) is observed owing to reduced reversibility caused by higher viscosity and precipitation of polymer chains (temperature of 80-100 degrees C).

The 6-amino-6-methyl-1,4-diazepine group as an ancillary ligand framework for neutral and cationic scandium and yttrium alkyls.

The 6-amino-6-methyl-1,4-diazepine framework is a readily available neutral 6-electron ligand moiety, suitable to support cationic group 3 metal alkyl catalysts; it also provides convenient access to tri- and tetradentate monoanionic ligand derivatives.

Neutral versus cationic Group 3 metal alkyl catalysts: performance in intramolecular hydroamination/cyclisation.

The relative catalytic activity of neutral dialkyl versus cationic monoalkyl Group 3 metal catalysts in the intramolecular hydroamination/cyclisation of the 2,2-dimethyl-4-pentenylamine reference substrate was investigated. This was found to depend strongly on the nature of the monoanionic ancillary ligand. With a bidentate amidinate ligand, the neutral catalysts were quite effective, but their cationic derivatives showed a much lower activity. The reaction kinetics suggest that this reflects an intrinsically higher activation barrier for the insertion of the olefinic moiety into the metal-amide bond for the cationic catalysts. In contrast, the neutral catalysts with tetradentate triamine-amide ligands showed a much lower activity than their cationic derivatives. It appears that this higher activity of the cationic triamine-amide catalysts reflects the beneficial effect of the additional available coordination space relative to the neutral species. The cationic triamine-amide yttrium catalysts are more active than the cationic amidinate catalysts of the same metal, possibly reflecting a stronger Y-amide bond in the latter, which is the more electron-deficient system.

Palladium-catalyzed enantioselective conjugate addition of arylboronic acids.

[reaction: see text] The first asymmetric palladium-catalyzed conjugate addition of arylboronic acids to alpha,beta-unsaturated aldehydes, ketones, and esters is described. For cyclic substrates, excellent chemo-, regio-, and enantioselectivities are achieved when a Pd(O2CCF3)2/DuPHOS catalyst is applied.

Naked (C5Me5)2M cations (M = Sc, Ti, and V) and their fluoroarene complexes.

The ionic metallocene complexes [Cp*(2)M][BPh(4)] (Cp* = C(5)Me(5)) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M = Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each contain one strongly distorted Cp* ligand, with one (V) or two (Ti) agostic C-H...M interactions involving the Cp*Me groups. For Sc and Ti, these Lewis acidic species react with fluorobenzene and 1,2-difluorobenzene to yield [Cp*(2)M(kappaF-FC(6)H(5))(n)][BPh(4)] (M = Sc, n = 2; M = Ti, n = 1) and [Cp*(2)M(kappa(2)F-1,2-F(2)C(6)H(4))][BPh(4)], the first examples of kappaF-fluorobenzene and kappa(2)F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C(6)F(5))(4)](-), both Sc and Ti form [Cp*(2)M(kappa(2)F-C(6)F(5))B(C(6)F(5))(3)] contact ion pairs. The nature of the metal-fluoroarene interaction was studied by density functional theory (DFT) calculations and by comparison with the corresponding tetrahydrofuran (THF) adducts and was found to be predominantly electrostatic for all metals studied.

Polyethene with pendant fullerene moieties.

Polyethene with fullerene moieties pendant on short-chain branches was prepared by the catalytic copolymerization of ethene and a fullerene-containing vinylic comonomer, yielding polyethene copolymers containing up to 25 wt% of C60.

Palladium-catalyzed copolymerization of ethene with acrolein dimethyl acetal: catalyst action and deactivation.

Acrolein dimethyl acetal (ADMA) can be copolymerized with ethene using a cationic alpha-diimine palladium chelate catalyst to yield branched copolymers. Catalyst deactivation occurs via methanol elimination to give an inert eta3-1-methoxyallyl palladium species. This process can be retarded by the addition of an aliquot of methanol to the reaction mixture, increasing overall catalyst productivity.

One ligand fits all: cationic mono(amidinate) alkyl catalysts over the full size range of the group 3 and lanthanide metals.

Using a sterically demanding amidinate ancillary ligand and an in situ alkylation procedure, neutral mono(amidinate) dialkyl and cationic mono(amidinate) monoalkyl complexes were prepared for metals spanning the full size range of the group 3 and lanthanide metals. The activity of the cationic monoalkyls in catalytic ethene polymerization was found to vary by over 2 orders of magnitude depending on the metal ionic radius, the intermediate metal sizes being found to be the most effective.

Application of monodentate secondary phosphine oxides, a new class of chiral ligands, in Ir(i)-catalyzed asymmetric imine hydrogenation.

Secondary phosphine oxides were prepared from R(1)PCl(2) and R(2)MgBr, followed by hydrolysis. They were obtained in an enantiopure form by preparative chiral HPLC. These new monodentate ligands were tested in the iridium-catalyzed hydrogenation of imines at 25 bar. Enantioselectivities up to 76% were obtained at L/Ir = 2. Addition of pyridine (Pyr/Ir = 1:2) raised the ee to 83%. Using pyridine as an additive allowed reduction of the L/Ir ratio to 1 without reduction of ee. [reaction: see text]

Yttrium alkyl complexes with a sterically demanding benzamidinate ligand: synthesis, structure and catalytic ethene polymerisation.

The benzamidinate yttrium dialkyl complexes [PhC(NAr)2]Y(CH2SiMe3)2(THF)n (Ar = 2,6-diisopropylphenyl; n = 1, 2) were prepared; when activated with [PhNMe2H][B(C6F5)4], the species with n = 1 polymerises ethene to polyethene with a narrow polydispersity.

Polyethene with pendant 3-thienyl functionalities.

Polyethene with 3-thienyl functionalities pendant on short-chain branches was prepared by catalytic random copolymerisation of ethene and 3-(penten-1-yl)thiophene; the functionalities can be used to graft poly(3-hexylthiophene) onto the polyethene surface.