Intermediacy of radicals in rearrangement and decomposition of metal-alkyl species: Relevance to metal-mediated polymerization of polar vinyl monomers

被引：16

作者：

Nagel, Megan ^{[1
]}

Sen, Ayusman ^{[1
]}

机构：

[1] Penn State Univ, Dept Chem, University Pk, PA 16802 USA

来源：

ORGANOMETALLICS | 2006年 / 25卷 / 20期

关键词：

D O I：

10.1021/om060519p

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The neutral compound [2,3-bis(2,6-diisopropylphenylimino)butane]Pd(CH2CH2CH2CO2Me)(X) (X = Cl, Br) undergoes "reverse" chain walking to form [2,3-bis(2,6-diisopropylphenylimino)butane]Pd(CH(CO2Me)CH2CH3)(X) through a conventional beta-hydrogen elimination/readdition pathway. However, reversible Pd-alkyl bond homolysis occurs for both alkyl complexes, and the resultant radicals can initiate the polymerization of acrylates.

引用

页码：4722 / 4724

页数：3

共 17 条

[1] Polymerization of acrylates by neutral palladium complexes.: Isolation of complexes at the initial steps [J].

Albéniz, AC ;

Espinet, P ;

López-Fernández, R .

ORGANOMETALLICS, 2003, 22 (21) :4206-4212

[2] Copolymerization of polar monomers with olefins using transition-metal complexes [J].

Boffa, LS ;

Novak, BM .

CHEMICAL REVIEWS, 2000, 100 (04) :1479-1493

[3] Palladium catalysed copolymerisation of ethene with alkylacrylates:: polar comonomer built into the linear polymer chain [J].

Drent, E ;

van Dijk, R ;

van Ginkel, R ;

van Oort, B ;

Pugh, RI .

CHEMICAL COMMUNICATIONS, 2002, (07) :744-745

[4] Palladium-based system for the polymerization of acrylates.: Scope and mechanism [J].

Elia, C ;

Elyashiv-Barad, S ;

Sen, A ;

López-Fernández, R ;

Albéniz, AC ;

Espinet, P .

ORGANOMETALLICS, 2002, 21 (20) :4249-4256

[5] Advances in non-metallocene olefin polymerization catalysis [J].

Gibson, VC ;

Spitzmesser, SK .

CHEMICAL REVIEWS, 2003, 103 (01) :283-315

[6] Late-metal catalysts for ethylene homo- and copolymerization [J].

Ittel, SD ;

Johnson, LK ;

Brookhart, M .

CHEMICAL REVIEWS, 2000, 100 (04) :1169-1203

[7] Mechanistic studies of the palladium-catalyzed copolymerization of ethylene and α-olefins with methyl acrylate [J].

Mecking, S ;

Johnson, LK ;

Wang, L ;

Brookhart, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (05) :888-899

[8] DFT studies on the copolymerization of α-olefins with polar monomers:: Ethylene-methyl acrylate copolymerization catalyzed by a Pd-based diimine catalyst [J].

Michalak, A ;

Ziegler, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (49) :12266-12278

[9] NOVEL POLYMERIZATION OF ALPHA-OLEFINS WITH THE CATALYST SYSTEM NICKEL AMINOBIS(IMINO)PHOSPHORANE [J].

MOHRING, VM ;

FINK, G .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1985, 24 (11) :1001-1003

[10] Metal-mediated polymerization of acrylates: Relevance of radical traps? [J].

Nagel, M ;

Paxton, WF ;

Sen, A .

MACROMOLECULES, 2004, 37 (25) :9305-9307

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