Dialkyl Complexes Research Articles

Half-Sandwich Cerium and Lanthanum Dialkyl Complexes: Synthesis, Structure, and Reactivity Studies.

Cerium and lanthanum dialkyl complexes [η5-1,2,4-(Me3C)3C5H2]Ln(CH2C6H4-o-NMe2)2 (Ln = Ce 1 and La 2), supported by a tri-tert-butylcyclopentadienyl ligand, have been successfully synthesized. Studies demonstrate that these complexes possess diverse reactivity toward various small molecules. For example, the reaction of complexes 1 and 2 with diphenyl dichalcogenides PhEEPh (E = S, Se) results in the formation of lanthanide thiolates [(η5-1,2,4-(Me3C)3C5H2)Ln(SPh)(μ-SPh)]2 (Ln = Ce 3 and La 4) and selenolates [(η5-1,2,4-(Me3C)3C5H2)Ln(SePh)(μ-SePh)]2 (Ln = Ce 5 and La 6), concomitantly releasing PhE(CH2C6H4-o-NMe2). Furthermore, complexes 1 and 2, upon reaction with dibenzyl disulfide, yield tetranuclear rare-earth metallomacrocyclic compounds {[(η5-1,2,4-(Me3C)3C5H2)Ln(μ-SCH2C6H5)]2(μ-η3:η3-SCHC6H5)}2 (Ln = Ce 7 and La 8). This reaction may involve a process of σ-bond metathesis and C-H activation. While the reaction of 1 and 2 with dibenzyl diselenide in the presence of LiCH2C6H4-o-NMe2 leads to the formation of lanthanide-lithium selenido clusters [(η5-1,2,4-(Me3C)3C5H2)La(μ-SeCH2C6H5)]3(μ3-Se)[μ3-SeLi(THF)3] (Ln = Ce 9 and La 10). Meanwhile, lanthanide selenido clusters [(η5-1,2,4-(Me3C)3C5H2)La(μ-SeCH2C6H4-o-NMe2)]4(μ3-Se)2 (Ln = Ce 11 and La 12) can be obtained by treating 1 and 2 with elemental selenium in a 1:2 molar ratio. Additionally, the treatment of 1 and 2 with benzoxazole generates ring-opening/C-C coupling/C-N coupling products {(η5-1,2,4-(Me3C)3C5H2)La[μ-OC6H4-o-N═CHN(CH(CH2C6H4-o-NMe2)2C6H4-o-O]}2 (Ln = Ce 13 and La 14). All new compounds were characterized by various spectroscopic methods, and their solid-state structures were confirmed by single-crystal X-ray diffraction analyses.

Regulating the photoluminescence of aluminium complexes from non-luminescence to room-temperature phosphorescence by tuning the metal substituents

Although luminescent aluminum compounds have been utilized for emitting and electron transporting layers in organic light-emitting diodes, most of them often exhibit not phosphorescence but fluorescence with lower photoluminescent quantum yields in the aggregated state than those in the amorphous state due to concentration quenching. Here we show the synthesis and optical properties of β-diketiminate aluminum complexes, such as crystallization-induced emission (CIE) and room-temperature phosphorescence (RTP), and the substituent effects of the central element. The dihaloaluminum complexes were found to exhibit the CIE property, especially RTP from the diiodo complex, while the dialkyl ones showed almost no emission in both solution and solid states. Theoretical calculations suggested that undesired structural relaxation in the singlet excited state of dialkyl complexes should be suppressed by introducing electronegative halogens instead of alkyl groups. Our findings could provide a molecular design not only for obtaining luminescent complexes but also for achieving triplet-harvesting materials.

Synthesis and Reactivity of the Rare-Earth Metal Complexes Bearing the Indol-2-yl-Based NCN Pincer Ligand.

The pincer rare-earth dialkyl complexes [κ3-LRE(CH2SiMe3)2 (RE = Lu(1a), Yb(1b), Er(1c), Y(1d), Dy(1e))] with the indol-2-yl-based NCN pincer ligand were synthesized by the reactions of the proligand HL (L = 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H4N) with RE(CH2SiMe3)3(THF)2. These complexes exhibited a variety of reactivities toward organic compounds such as amines, triphenylphosphine ylide, N-phenylimidazole, pyridine derivatives, and o-carborane leading to σ-bond metathesis, migration insertion, and redox reaction products. The reactions of the dialkyl rare-earth metal complexes with o-carborane afforded the novel NCN pincer-ligated carboryne-based metallacyclopropanes which reacted with diphenyl ketone to give insertion products of the RE-C2-ind and one of the RE-Ccage bonds, while the reaction of the carboryne-based metallacyclopropanes with diphenyldiazomethane produced the di-aza-metallacyclopentanes via the insertions of the N═N bond of the diphenyldiazomethane into two RE-Ccage bonds and the RE-C2-ind bond. The reactions of the dialkyl complexes with 2 equiv of 2,2'-bipyridine afforded the pincer-ligated bis(2,2'-bipyridyl monoanionic radical) complexes via the homolytic redox reaction.

Synthesis, characterization of indol-2-yl-based NCO pincer rare-earth metal alkyl complexes and their catalytic activity towards hydroboration of imines

The reactions of HL (L = 1-(CH3OCH2CH2)-3-(Me2NCH2)-C8H4N) with different equivalent of the RE(CH2SiMe3)3(THF)2 produced a series of novel indol-2-yl-based NCO pincer rare-earth metal dialkyl complexes (κ3NCO-L)RE(CH2SiMe3)2 (RE = Lu(1a), Yb(1b)) and monoalkyl complexes (κ2NC-L)(κ3NCO-L)RE(CH2SiMe3) (RE = Lu(2a), Yb(2b), Er(2c), Y(2d)). These complexes served as catalysts for the hydroboration of imines and exhibited excellent activity with high efficiency under solvent-free and ambient temperature conditions.

Synthesis of bis(oxazoline)-based rare-earth metal complexes and their catalytic performance in the polymerization of isoprene and polar ortho-methoxystyrene.

A series of bis(oxazoline) rare-earth metal dialkyl complexes [(L)Ln(CH2SiMe3)2(THF)n] (L = L1 (dimethyl-substituted bis(oxazoline) ligand), Ln = Y (1-Y), Lu (1-Lu), Sc (1-Sc), n = 1; L = L2 (phenyl-substituted bis(oxazoline) ligand), Ln = Y (2-Y), Lu (2-Lu), Sc (2-Sc), n = 2) was successfully prepared. NMR spectroscopy and X-ray diffraction indicated that all the complexes ligated with a C2 symmetric bis(oxazoline) and two trimethylsilylmethyl ligands. In the presence of borate and triisobutyl aluminium, these complexes exhibited high catalytic activity for the polymerization of isoprene, yielding the polymer with high cis-1,4-regularity (up to 99.9%) and high molecular weight. Moreover, these ternary catalytic systems also served as efficient initiators for the polymerization of polar ortho-methoxystyrene. However, atactic polymers in all the cases were isolated despite the C2 symmetric geometry of bis(oxazoline) ligands.

Synthesis of diaryl dithiocarbamate complexes of zinc and their uses as single source precursors for nanoscale ZnS

Diaryldithiocarbamate complexes, [Zn(S2CNAr2)2], have been prepared with a view to comparing their structures, reactivity and thermally-promoted degradation with respect to the well-studied dialkyl-derivatives. In the solid-state both [Zn{S2CN(p-tol)2}2] and [Zn{S2CN(p-anisyl)2}2] are monomeric with a distorted tetrahedral Zn(II) centre, but somewhat unexpectedly, the bulkier naphthyl-derivative [Zn{S2CN(2-nap)2}2]2 forms dimeric pairs with five-coordinate Zn(II) centres. Preliminary reactivity studies on [Zn{S2CN(p-tol)2}2] suggests that it binds amines and cyclic amines in a similar fashion to the dialkyl complexes and can achieve six-coordination as shown in the molecular structure of [Zn{S2CN(p-tol)2}2(2,2′-bipy)]. The thermal decomposition of [Zn{S2CN(p-tol)2}2] was studied in oleylamine solution by both heat-up and hot-injection methods. Nanorods of ZnS were produced in both cases with average dimensions of 17 × 2.1 nm and 11 × 3.5 nm respectively, being significantly shorter than those produced from [Zn(S2CNiBu2)2] under similar conditions. This is tentatively attributed to the differing rates of amine-exchange between diaryl- and dialkyl dithiocarbamate (DTC) complexes and/or their differing rates of DTC loss following amine-exchange. The solid-state decomposition of [Zn{S2CN(p-tol)2}2] has also been studied at 450 °C under argon affording irregular and large (10–300 µm) sheet-like particles of wurtzite.

Rare-earth metal complexes supported by indolyl-based NCN-pincer ligand and their efficient catalysis for isoprene polymerization

Rare-earth metal dialkyl complexes [1-CH2N(CH3)2–3-CH2CH2N(CH3)2C8H4N]RE(CH2SiMe3)2 (RE = 1-Y, 2-Er, 3-Yb and 4-Lu) were synthesized by the well-designed indolyl-based proligand 1-CH2N(CH3)2–3-CH2CH2N(CH3)2C8H4NH with rare-earth metal trialkyl complexes (RE(CH2SiMe3)2(THF)2) underwent direct alkane elimination. Single-crystal X-ray analyses and the NMR spectroscopy revealed these dialkyl complexes were analogous mononuclear NCN-pincer geometry via CH activation of 2-sp2 indole. Employing these complexes, upon activation by aluminum alkyls and borate, initiated isoprene polymerization with high conversion and high stereoselectivity (98% conversion of 2000 equivalent of isoprene, 1,4-cis polymers up to 91.5%).

Group 3 dialkyl complexes of a rigid monoanionic NNN-donor pincer ligand: synthesis, structures, unexpected reactivity with CPh3+, and hydroamination catalysis.

Palladium-catalyzed coupling of 4,5-dibromo-2,7,9,9-tetramethylacridan with two equivalents of 1,3-diisopropylimidazolin-2-imine afforded 4,5-bis(1,3-diisopropylimidazolin-2-imino)-2,7,9,9-tetramethylacridan, H[AII2]. Reaction of the H[AII2] pro-ligand with one equivalent of [M(CH2SiMe3)3(THF)2] (M = Y or Sc) yielded the base-free neutral dialkyl complexes [(AII2)M(CH2SiMe3)2] {M = Y (1) and Sc (2)}. The rigid AII2 pincer ligand affords a similar steric profile to the previously reported XA2 pincer ligand, but is monoanionic rather than dianionic. Reaction of 1 with one equiv. of [CPh3][B(C6F5)4] in C6D5Br generated a highly active catalyst for intramolecular alkene hydroamination. However, rather than forming the expected monoalkyl cation, this reaction afforded a diamagnetic product which was identified as [(AII2-CH2SiMe3)Y(CH2SiMe3)2][B(C6F5)4] (3; AII2-CH2SiMe3 is a neutral tridentate ligand with a central amine donor flanked by imidazolin-2-imine groups) in approx. 20% yield, accompanied by HCPh3 (∼2 equiv. relative to 3), an unidentified paramagnetic product (detected by EPR spectroscopy), and a small amount of colourless precipitate. The unexpected reactivity of 1 with CPh3+ is thought to involve initial AII2 ligand backbone oxidation, given that the zwitterionic form of the ligand contains a phenylene ring with two adjacent anionic nitrogen donors, similar to a redox-non-innocent, dianionic ortho-phenylenediamido ligand.

Rare earth dialkyl cations and monoalkyl dications supported by a rigid neutral pincer ligand: synthesis and ethylene polymerization.

A palladium-catalyzed coupling reaction between 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylxanthene and 2 equiv. of 1,3-diisopropylimidazolin-2-imine afforded the rigid neutral 2,7-di-tert-butyl-4,5-bis(1,3-diisopropylimidazolin-2-imino)-9,9-dimethylxanthene (XII2) pincer ligand. Reaction of XII2 with YCl3(THF)3.5 provided [(XII2)YCl3] (1). However, compound 1 failed to react cleanly with 3 equiv. of LiCH2SiMe3, and the reaction of XII2 with [Y(CH2SiMe3)3(THF)2] afforded a complex mixture of products. To access group 3 alkyl complexes without the intermediacy of [(XII2)M(CH2SiMe3)3], the XII2 ligand was protonated using [H(OEt2)2][B(C6F5)4] to form [H(XII2)][B(C6F5)4], and subsequent reaction with [M(CH2SiMe3)3(THF)2] (M = Y, Sc) directly afforded the cationic scandium and yttrium dialkyl complexes [(XII2)M(CH2SiMe3)2][B(C6F5)4] {M = Y (2) and Sc (3)}. Reaction of 3 with B(C6F5)3 in C6D5Br afforded dicationic [(XII2)Sc(CH2SiMe2CH2SiMe3)][MeB(C6F5)3][B(C6F5)4] (4) featuring a CH2SiMe2CH2SiMe3 ligand, formed as a result of methyl anion abstraction from silicon, with concomitant migration of the neighbouring CH2SiMe3 group from scandium to silicon. The MeB(C6F5)3 anion in 4 forms a contact ion pair. By contrast, reaction of 1 with [CPh3][B(C6F5)3] in C6D5Br/toluene or o-C6H4F2/toluene afforded dicationic [(XII2)Sc(CH2SiMe3)(ηx-toluene)n][B(C6F5)4]2 (5). Compounds 2-4 showed negligible ethylene polymerization activity, whereas 5 is highly active (up to 870 kg mol-1 h-1 atm-1 in o-C6H4F2/toluene under 1 atm of ethylene at room temperature).

Oxygen transfer reactivity mediated by nickel perfluoroalkyl complexes using molecular oxygen as a terminal oxidant.

Nickel perfluoroethyl and perfluoropropyl complexes supported by naphthyridine-type ligands show drastically different aerobic reactivity from their trifluoromethyl analogs resulting in facile oxygen transfer to perfluoroalkyl groups or oxygenation of external organic substrates (phosphines, sulfides, alkenes and alcohols) using O2 or air as a terminal oxidant. Such mild aerobic oxygenation occurs through the formation of spectroscopically detected transient high-valent NiIII and structurally characterized mixed-valent NiII-NiIV intermediates and radical intermediates, resembling O2 activation reported for some Pd dialkyl complexes. This reactivity is in contrast with the aerobic oxidation of naphthyridine-based Ni(CF3)2 complexes resulting in the formation of a stable NiIII product, which is attributed to the effect of greater steric congestion imposed by longer perfluoroalkyl chains.

Vanadium-catalysed regioselective hydroboration of epoxides for synthesis of secondary alcohols.

Regioselective epoxide ring-opening through hydroboration catalysed by a vanadium(III) dialkyl complex supported by a redox-active terpyridine ligand is reported. Secondary alcohols were obtained in high yields via effective Markovnikov hydroboration of terminal epoxides, showcasing a new catalytic application of an earth-abundant vanadium(III) complex.

Rare-Earth Metal Complexes Supported by 1,3-Functionalized Indolyl-Based Ligands for Efficient Hydrosilylation of Alkenes

Two different 1,3-functionalized indolyl-based proligands 1-(2-C4H7O)CH2-3-(2-tBuC6H5N═CH)C8H5N (HL1) and 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H5N (HL2) were designed, prepared in high yields, and successfully applied to rare-earth metal chemistry showing different reactivities and different bondings with the central metals. The reactions of HL1 with RE(CH2SiMe3)3(THF)2 provided two types of rare-earth metal complexes: the pincer type mononuclear complexes κ3-(L1)RE(CH2SiMe3)2 [L1 = 1-(2-C4H7O)CH2-3-(2-tBuC6H5N═CH)C8H4N, RE = Lu(1), Yb(2)], and the dinuclear rare-earth metal alkyl (per alkyl/per metal) complexes having the ligand in novel coordination modes {(η1:(μ-η2:η1):η1-1-(2-C4H7O)CH2-3-[2-tBuC6H5NCH-(CH2SiMe3)]C8H4N)RECH2SiMe3}2 [RE = Er(3), Y(4), Dy(5), and Gd(6)]. Meanwhile, the reactions of HL2 with RE(CH2SiMe3)3(THF)2 led to the isolation and characterization of only the mononuclear rare-earth metal dialkyl complexes κ3-(L2)RE(CH2SiMe3)2 [L2 = 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H4N, RE = Lu(7), Gd(8)] bearing the ligand in the pincer chelate form. The mononuclear complexes were formed through the sp2 C-H activation of the 2-indolyl moiety, while the dinuclear complexes were produced unexpectedly through the tandem 2-indolyl sp2 C-H activation and C═N insertion into the RE-CH2SiMe3 bond. These complexes were fully characterized by spectroscopic methods, elemental analyses, and single-crystal X-ray crystallography. The applications of the synthesized complexes as catalysts for the hydrosilylation of terminal alkenes with phenylsilane are described. Anti-Markovnikov addition products were produced by the hydrosilylation of aliphatic olefins, and Markovnikov addition products were isolated with aromatic olefins with high selectivity in the absence of cocatalysts. It is found that the dinuclear rare-earth alkyl complexes exhibited the best catalytic activity with the advantages of mild reaction conditions, short reaction time, low catalyst loading, and wide substrate applicability in comparison with the synthesized mononuclear complexes and the reported catalysts.

Rare-Earth-Metal-Complex-Catalyzed Hydroalkoxylation and Tandem Hydroalkoxylation/Cyclohydroamination of Isocyanates: Synthesis of Carbamates and Oxazolidinones.

Novel N,N,N-tridentate β-diketiminato rare-earth-metal dialkyl complexes LRE(CH2SiMe3)2 [RE = Y (1a), Gd (1b), Yb (1c), Lu (1d); L = MeC(NDipp)CHC(Me)N(CH2)2NC4H8, where Dipp = 2,6-iPr2C6H3] have been conveniently synthesized by one step from reactions of the rare-earth-metal trialkyl complexes RE(CH2SiMe3)3(THF)2 (THF = tetrahydrofuran) with a pyrrolidine-functionalized β-diketiminate HL, and their catalytic behaviors toward hydroalkoxylation and tandem hydroalkoxylation/cyclohydroamination of isocyanates have been described. These rare-earth-metal catalysts exhibited high efficiency in the hydroalkoxylation of isocyanates, providing a variety of N-alkyl and N-aryl carbamate derivatives under mild reaction conditions with a rather low catalyst loading (0.04 mol %). More significantly, they can promote a tandem hydroalkoxylation/cyclohydroamination reaction between terminal and internal propargylic alcohols with substituted arylisocyanates, leading to the efficient synthesis of methylene and (Z)-selective arylidene oxazolidinones in good-to-high yields via consecutive C-O and C-N bond formation. The stoichiometric reaction of 1a with p-tolylisocyanate generated an unusual dinuclear yttrium complex, {[η2-(4-MePhNCO)(CH2SiMe3)]Y[μ-η2:η1:η1-(4-MePhNCO)CC(Me)(NDipp)C(Me)N(CH2)2NC4H8]}2 (7a), with two different amidate units, which underwent an sp2 C-H bond activation of the β-diketiminato backbone, followed by the insertion of isocyanate.

Scandium, titanium and vanadium complexes supported by PCP-type pincer ligands: synthesis, structure, and styrene polymerization activity.

A series of first-row early transition metal dialkyl complexes bearing pincer ligands [(POCOP)M(CH2SiMe3)2] (POCOP: (2,6-(tBu2PO)2-C6H3); 1-Sc: M = Sc; 1-Ti: M = Ti; 1-V: M = V) and [(PCP)M(CH2SiMe3)2] (PCP: (2,6-(tBu2PCH2)2-C6H3); 2-Sc: M = Sc; 2-Ti: M = Ti) have been synthesized. These dialkyl complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy, and solution magnetic susceptibility (Evans method) analyses appropriately. All the complexes exhibited square pyramidal geometries with different extents of distortion. The activities of these complexes were further explored in styrene polymerization, in which combinations of scandium complexes (1-Sc or 2-Sc) with [Ph3C][B(C6F5)4] were found to be active catalytic systems for highly syndiospecific (>99% rrrr) polymerization of styrene. Meanwhile, the Ti(III) complexes 1-Ti and 2-Ti showed rather low activity in styrene polymerization, which stands in sharp contrast to those in previous reports involving Ti(III) catalysts bearing cyclopentadienyl derivative ligands.

Synthesis and Structure Diversity of Half‐Sandwich Rare Earth Dialkynyl Complexes

AbstractHalf‐sandwich rare‐earth dialkynyl complexes are of much interest in both structure and reactivity but have remained much underexplored to date. Here we report the synthesis and transformation of a new family of half‐sandwich dialkynyl complexes bearing the C5Me4SiMe3 ligand, which exhibited diverse structural features depending on metal ion size, alkyne substituent and with or without THF coordination. The acid‐base reactions between half‐sandwich rare earth dialkyl complexes (C5Me4SiMe3)Ln(CH2SiMe3)2(THF) (Ln=Sc, Y, Lu) and two equivalents of terminal alkynes such as phenylacetylene and trimethylsilylacetylene in THF generally gave the corresponding THF‐coordinated monomeric rare earth dialkynyl complexes, which upon recrystallization from toluene yielded further aggregated alkynyl complexes with partial or full dissociation of the THF ligands. In the case of phenylacetylene, trimeric yttrium and lutetium hexaalkynyl complexes were formed, in which each pair of the metal atoms was bridged by two alkynyl ligands in solid state but the alkynyl ligands underwent rapid site exchange in toluene solution. In the case of trimethylsilylacetylene with yttrium and lutetium, dimeric tetraalkynyl complexes bearing two terminal and two bridging alkynyl ligands were obtained from toluene. In contrast, recrystallization of the scandium trimethylsilylacetylide complex from toluene induced alkynyl coupling and yielded dimeric scandium complex with one butatrienediyl and two alkynyl bridging ligands. Upon dissolution in THF, all the aggregated alkynyl/butatrienediyl complexes were rapidly reconverted to the monomeric dialkynyl complexes as a result of THF coordination to the rare earth metal atoms.

Well-defined phosphate yttrium dialkyl complexes for catalytic stereo-controllable 1,4-polymerization of isoprene

Oxygen ligation is envisioned to provide a stable and distinctive coordination environment to the strongly oxophilic rare-earth metals. However, the well-defined dialkyl complexes bearing oxyanion ancillary ligand had been rarely addressed for the instability of the complexes and the shortage of easily available ligands. Herein, we report the synthesis of phosphate ligated dialkyl yttrium complexes (PYR2) featuring a high stability and a tunable ligand. Treated with the borate reagent, the phosphate yttrium complex displays high activity and selectivity in the catalytic cis-1,4-polymerization of isoprene (up to 96.5%). Furthermore, using AlMe3 as an additive, the stereoselectivity switches to trans-1,4-polymerization (up to 92.0%).

N-heterocyclic carbene stabilized indenyl scandium di-alkyl complex: Preparation of ultra-high molecular weight polyolefin

By using iPr2Im as a Lewis base ligand, β-H elimination reactions of propylene polymerization were suppressed at −30 °C. Polypropylene and its block copolymers with ethylene possessing ultra-high molecular weights (Mn > 1,000,000 g/mol) were successfully obtained in high TOFs (PP > 104 mol molSc−1 h−1). DFT calculations suggested that the delocalized electrons in the strongly conjugated system of iPr2Im could significantly reduce the electro positivity of active sites. This method provides a convenient strategy for tuning the electronic properties of active sites.

DMAO-activated Rare-earth Metal Catalysts for Styrene and Its Derivative Polymerization

The catalytic performance of rare-earth metal dialkyl complexes in combination with DMAO (dry methylaluminoxane) is explored. In the presence of 60 equivalents of DMAO, the half-sandwich complex (C13H8CH2Ph)Sc(CH2SiMe3)2(THF) (1) is inert for styrene polymerization, but (C5Me4Ph)Sc(CH2C6H4NMe2-o)2 (2) converts 18% styrene into syndiotactic polystyrene. Under the same conditions, the constrained-geometry configuration sandium complex (C13H8CH2Py)Sc(CH2SiMe3)2 (3a) displays extremely high catalytic activity (> 6420 kg·molSc−1 h−1) and perfect syndiospecific (rrrr > 99%) for styrene polymerization, and, in contrast, its lutetium (3b) and yttrium (3c) analogues are nearly inactive. Although the binary catalytic system 3a/DMAO exhibits very low activity for 4-methoxystyrene polymerization, it is an efficient catalyst for the syndioselective polymerization of other styrene derivatives such as 2-methoxystyrene, 4-methylthiostyrene, 4-fluorostyrene, 4-dimethylhydrosilylstyrene, alkyne-susbstituted styrenes and 4-methylstyrene. In addition, the binary system 3a/DMAO can copolymerize ethylene and styrene to give alternating copolymers with a single glass transition at 80 °C and 4 bar ethylene pressures. On increasing styrene feed amount from 20 to 60 mmol, the styrene content slight increases from 48.2 mol% to 53.8 mol%, but the polymerization activity is obviously promoted from 240 to 532 kg molSc–1·h–1.

Synthesis of Cyclic Polyolefin: Ring‐Opening Metathesis Polymerization by Binuclear Vanadium Complexes†

Main observation and conclusionRing‐opening metathesis polymerization (ROMP) of norbornene by binuclear vanadium alkylidene in‐situ formed from dialkyl complexes was investigated. Higher activities were observed by the binuclear system than mononuclear analogues. Especially the cyclic polymers were obtained and demonstrated. It is proposed that cyclic binuclear vanadium alkylidene was afforded due to the intramolecular chain‐transfer reaction. The size of polymer ring could be adjusted by the vanadium catalyst structure and polymerization temperature. Similar results were also observed in the ROMP of cyclopentene.

Synthesis and Asymmetric Alkene Hydrogenation Activity of C2-Symmetric Enantioenriched Pyridine Dicarbene Iron Dialkyl Complexes

Enantioenriched N-alkyl-imidazole-substituted pyridine dicarbene iron dialkyl complexes have been synthesized and characterized by 1H NMR and zero-field 57Fe Mossbauer spectroscopies as well as sin...