Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes
文献类型：期刊论文
| 作者 | Rong WF ; Liu DT ; Zuo HP ; Pan YP ; Jian ZB ; Li SH ; Cui DM |
| 刊名 | organometallics
 |
| 出版日期 | 2013 |
| 卷号 | 32期号:5页码:1166-1175 |
| ISSN号 | 0276-7333 |
| 关键词 | RING-OPENING POLYMERIZATION STEREOSPECIFIC ISOPRENE POLYMERIZATION LANTHANIDE ALKYL COMPLEXES X-RAY-STRUCTURE BOROHYDRIDE COMPLEXES EPSILON-CAPROLACTONE SELECTIVE POLYMERIZATION NEODYMOCENE CATALYST BIS(ALKYL)S BEARING PRE-CATALYST |
| 通讯作者 | cui dm |
| 中文摘要 | the bis-arylated phosphazene compounds [hn(pph2nar)(2)] (ar = phenyl (hl1), 2,6-dimethylphenyl (hl2), 2,6-diisopropylphenyl (hl3)) and the imidodiphosphinate compound hn(pph2o)(2) (hl4) have been prepared via the staudinger reaction. treatment of the neutral compounds hl1, hl2, and hl3 with ln(ch2sime3)(3)(thf)(2) (ln = sc, y, lu) generated the solvent-free bis(alkyl) complexes l(1)ln(ch2sime3)(2) (ln = sc (1a), y (1b), lu (1c)), (lsc)-sc-2(ch2sime3)(2) (2a), (ly)-y-3(ch2sime3)(2) (3b), and (llu)-lu-3(ch2sime3)(2) (3c), respectively. the reaction between hl4 and y(ch2sime3)(2)(thf)(2) gave the rare zwitterionic complex 4b. lithiation of the ligand hl1 by nbuli followed by a metathesis reaction with nd(bh4)(3)(thf)(3) afforded the corresponding complex (lnd)-nd-1(bh4)(2)(thf)(2) (5). complexes 1 upon incorporation of [ph3c] [b(c6f5)(4)] and alibu(3) led to ternary systems that initiated isoprene polymerization with high activities, among which complex 1a was the first example of a scandium catalytic precursor providing trans-1,4-selectivity (90.0%), while the lutetium analogue 1c had medium trans-1,4-selectivity (54.3%) and the yttrium complex 1b exhibited high cis-1,4-selectivity (76.3%). the ternary system based on the zwitterion 4b displayed the highest activity for the isoprene polymerization among these complexes and gave cis-1,4-regularity-enriched polyisoprene (70.6%). highly stereospecific homopolymerizations of isoprene (trans-1,4-content: 97.0%) and butadiene (trans-1,4-content: 94.0%) were achieved by using the borohydrido complex 5 upon the activation of dibutylmagnesium. the copolymerization of isoprene and butadiene with 1a/[ph3c][b(c6f5)(4)/alibu(3)] gave randomly arranged trans-1,4-regulated polybutadiene and polyisoprene sequences. the kinetics study displayed competitive polymerization rates of r(bd) = 2.89 and r(ip) = 0.41. the thermal behaviors of the (co)polymers were investigated. |
| 收录类别 | SCI收录期刊论文 |
| 语种 | 英语 |
| WOS记录号 | WOS:000316094900006 |
| 公开日期 | 2014-04-16 |
| 源URL | [http://ir.ciac.jl.cn/handle/322003/49982]  |
| 专题 | 长春应用化学研究所_长春应用化学研究所知识产出_期刊论文 |
| 推荐引用方式 GB/T 7714 | Rong WF,Liu DT,Zuo HP,et al. Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes[J]. organometallics,2013,32(5):1166-1175. |
| APA | Rong WF.,Liu DT.,Zuo HP.,Pan YP.,Jian ZB.,...&Cui DM.(2013).Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes.organometallics,32(5),1166-1175. |
| MLA | Rong WF,et al."Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes".organometallics 32.5(2013):1166-1175. |
入库方式： OAI收割
来源：长春应用化学研究所
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