Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes

doi:10.1021/om300967h

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	Rare-Earth-Metal Complexes Bearing Phosphazene Ancillary Ligands: Structures and Catalysis toward Highly Trans-1,4-Selective (Co)Polymerizations of Conjugated Dienes
	Rong, Weifeng 1,2; Liu, Dongtao 1; Zuo, Huiping 3; Pan, Yupeng 1,2; Jian, Zhongbao 1,2; Li, Shihui 1; Cui, Dongmei 1
刊名	ORGANOMETALLICS
	2013-03-11
卷号	32 期号:5 页码:1166-1175
ISSN号	0276-7333
DOI	10.1021/om300967h
英文摘要	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.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000316094900006
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/54911]
专题	中国科学院化学研究所
通讯作者	Cui, Dongmei
作者单位	1.Chinese Acad Sci, State Key Lab Polymer Phys & Chem, Changchun Inst Appl Chem, Changchun 130022, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China 3.Jilin Univ, Sch Chem, Changchun 130012, Peoples R China
推荐引用方式 GB/T 7714	Rong, Weifeng,Liu, Dongtao,Zuo, Huiping,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, Weifeng.,Liu, Dongtao.,Zuo, Huiping.,Pan, Yupeng.,Jian, Zhongbao.,...&Cui, Dongmei.(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, Weifeng,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.