ConspectusThe search for new catalysts more efficient, selective chemical transformations and the synthesis of functional materials has been a long-standing research subject in both academia industry. To develop generations that are superior or complementary to existing ones, exploring potential untapped elements is an important strategy. Rare-earth elements, including scandium, yttrium, lanthanides (La–Lu), constitute one frontier periodic table. possess unique physical properties different...

Abstract The regioregular synthesis of the first azaborine oligomers and a corresponding conjugated polymer was accomplished by Suzuki–Miyaura coupling methods. An almost perfectly coplanar syn arrangement heterocycles deduced from an X‐ray crystal structure dimer, which also suggested that NH⋅⋅⋅π interactions play important role. Computational studies further supported these experimental observations indicated electronic longer resembles poly(cyclohexadiene) more than poly( p ‐phenylene)....

A series of polymers (PBnT, n = 2–5) with boron atoms incorporated into the conjugated polythiophene main chain have been prepared via Pd-catalyzed coupling stannylated thienylborane monomers. The exhibit excellent long-term chemical stability to air and moisture remarkable thermal decomposition temperatures reaching over 300 °C. high is achieved by placing very bulky pendant groups, 2,4,6-tri-tert-butylphenyl (Mes*) 2,4,6-tris(trifluoromethyl)phenyl (FMes), on that prevent attack...

Regioselective electrophilic borylation of a pyridyl-flanked fluorene provides highly luminescent, air-stable boron-bridged ladder species.

The polymerization of 1,5-hexadiene (HD) and its copolymerization with styrene ethylene by a series half-sandwich scandium dialkyl complexes bearing various auxiliary ligands have been examined. Significant ligand influence on the catalytic activity selectivity has observed. THF-free aminobenzyl complex sterically demanding ligand, such as (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 (4e), in combination an equivalent [Ph3C][B(C6F5)4], serves excellent catalyst for cyclocopolymerization HD to afford new...

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication the EditorNEXTCycloterpolymerization of 1,6-Heptadiene with Ethylene and Styrene Catalyzed by a THF-Free Half-Sandwich Scandium ComplexFang Guo†‡, Masayoshi Nishiura‡, Hiroyuki Koshino‡, Zhaomin Hou*†‡View Author Information† The State Key Laboratory Fine Chemicals, School Chemical Engineering, Dalian University Technology, 116012, China‡ Organometallic Chemistry Advanced Catalyst Research Team, RIKEN Science Institute,...

Amino-containing functionalized syndiotactic polystyrenes with high melting temperatures and temperature stability are synthesized by the direct polymerization of amino-containing styrenic monomers in presence a half-sandwich scandium catalyst system [(C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2]/[Ph3C][B(C6F5)4]. The poly(N,N-dimethylamino)styrene (rrrr > 99%), then used as novel polymer supports, effectively anchored Pd nanoparticles (3 wt % Pd) diameter 4 or 5 nm that were uniformly dispersed on matrix.

Abstract The regioregular synthesis of the first azaborine oligomers and a corresponding conjugated polymer was accomplished by Suzuki–Miyaura coupling methods. An almost perfectly coplanar syn arrangement heterocycles deduced from an X‐ray crystal structure dimer, which also suggested that NH⋅⋅⋅π interactions play important role. Computational studies further supported these experimental observations indicated electronic longer resembles poly(cyclohexadiene) more than poly( p ‐phenylene)....

Air- and water-stable, π-conjugated [−donor–acceptor−]n oligomers containing thiophene fragments as donors 9,10-dimesityl-9,10-dihydro-9,10-diboraanthracene (DBA(Mes)2) acceptor units were prepared through Stille-type C–C-coupling protocols. The reaction between 2,6-dibromo-DBA(Mes)2 (1), 2,7-dibromo-DBA(Mes)2 (2), 2-bromo-6,7-dimethyl-DBA(Mes)2 (3), 2,5-bis(trimethylstannyl)thiophene (7) furnished monodisperse, short-chain model systems 80 (2 × DBA(Mes)2, 1 2,5-thienylene) 81 (3 2 after GPC...

In our quest to develop regioregular borane acceptor-modified thiophene polymers, we prepared a series of new alkynylphenylborane-functionalized monomers and explored their polymerization. The polymer rr-P1 an alternating copolymer with 3-hexylthiopene, rr-P2, were successfully obtained by Stille-type An X-ray crystal structure the bithiophene model system 2-Br revealed coplanar rings formation π-stacks, despite presence bulky dimesitylborane moieties. For showed most bathochromic absorption...

The polymerization of halide-substituted styrenes (XSt) and their copolymerization with styrene by half-sandwich scandium catalysts without a THF ligand have been examined. THF-free aminobenzyl complex (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 (2) in combination 1 equiv [Ph3C][B(C6F5)4] showed high activity excellent syndiotacticity for the (XSt = p-, o-, m-ClSt, p-FSt, p-BrSt, p-ISt). Despite presence electron-withdrawing halogen substituent on aromatic ring, reached up to 105 g polymer molSc–1 h–1...

We have designed and synthesized the first examples of 7-membered diazaphosphepines using phosphorus-amine (P-N) chemistry. Different from previous functional protocols heteropines, installation π-conjugated substituents having diverse chemistries at [d]-C[double bond, length as m-dash]C double bond position heteropine core allows us to effectively control chemical electronic structures in both ground excited states these diazaphosphepines. This functionalization has led a set crystal...

A novel family of myrcene-based polyolefins and functionalized was prepared by the copolymerization myrcene with ethylene propylene catalyzed half-sandwich scandium complexes.

Abstract Palladium nanoparticles immobilized on an amino‐functionalized syndiotactic polystyrene ( s PS‐N) served as a novel recyclable catalyst for the dimethylation and cross methyl alkylation of wide range ketones with methanol methylation agent. This heterogeneous (Pd@ was highly robust showed excellent thermal stability chemical resistance. It not only remarkably high activity, but it could also be easily recovered by filtration without loss activity.

Abstract N ‐methylation of amines is one the most important C−N bond‐forming reactions and widely utilized for synthesis numerous agrochemicals, drugs, natural products, dyes. In this paper, ‐monomethylation aniline derivatives using Pd/C catalyst methanol as methylation reagent was investigated. The various anilines achieved with high activity selectivity under relatively mild reaction conditions, yield ‐monomethyl over 90 %. Notably, commercial, readily available, inexpensive heterogeneous...

A series of half-sandwich scandium-dialkyl complexes that bear various auxiliary ligands have been examined for the copolymerization isoprene (IP) with nonconjugated α,ω-dienes such as 1,5-hexadiene (HD) and 1,6-heptadiene (HPD). Significant ligand influence on catalytic activity selectivity has observed. The thf-coordinated complex [(C5Me4SiMe3)Sc(CH2SiMe3)2(thf)] (2) methoxy side arm containing [(C5Me4C6H4OMe-o)Sc(CH2SiMe3)2] (3), in combination an equivalent [Ph3C][B(C6F5)4], can serve...

Stereoregular star polymers were synthesized through an “arm-first” approach <italic>via</italic> a living coordination polymerization mechanism for the first time using half-sandwich scandium catalyst system.

A novel family of well-designed thermoreversible polyepichlorohydrin elastomers with furan/maleimide covalent crosslinks possessed excellent mechanical, self-healing ability and recyclability.

DFT calculations disclosed that the stereoselectivity of Sc-catalysed polymerization halogenated styrenes could be co-regulated via C-Hπ interactions between a coordinating THF and phenyl ring monomer. Such regulatory mechanism was theoretically confirmed by further studying various monomers, where even shift from syndiotacticity to isotacticity.

Amino-functionalized crystalline styrenic thermoplastic elastomers were prepared by carrying out stereoselective copolymerizations of 4-(<italic>N</italic>,<italic>N</italic>-diphenylamino)styrene and isoprene with the use a C₅H₅-ligated scandium catalyst.

Abstract Palladium nanocatalyst supported on dimethylamino‐functionalized syndiotactic polystyrene (Pd@ s PS‐NMe 2 ) showed high activity and selectivity for the N ‐monomethylation of various primary amines using methanol as methylation reagent under air. The excellent catalytic performance could be associated with ultrafine palladium nanoparticles amine‐adsorbing capacity catalyst. Pd@ catalyst was highly robust, easily recovered by filtration reused more than ten times without decrease in...

A novel family of ethylene–propylene–isoprene terpolymers was prepared by the terpolymerization ethylene and propylene with isoprene catalyzed half-sandwich scandium complexs.

This paper demonstrated fluorescence behaviour of two novel coumarin-containing dendrigraft polybutadienes (PB-Cou) with linear-comb (LC-PB-Cou) and star-comb (SC-PB-Cou) architectures. LC-PB-Cou SC-PB-Cou 12–13 mol% coumarin content were synthesized via the combination anionic polymerization "click" chemistry methodology. The photophysical behaviours investigated based on UV-Vis spectroscopy spectroscopy. tailor-made designed to possess almost identical branching parameters except for...