E-H (E = B, Si, Ge) bond activation of pinacolborane, silanes, and germanes by nucleophilic palladium carbene complexes

被引：47

作者：

Comanescu, Cezar C. ^{[1
]}

Iluc, Vlad M. ^{[1
]}

机构：

[1] Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA

来源：

CHEMICAL COMMUNICATIONS | 2016年 / 52卷 / 58期

关键词：

TRANSITION-METAL-COMPLEXES; RECENT PROGRESS; REACTIVITY; LIGAND; HYDROSILYLATION; METHANDIIDE; ELIMINATION; COOPERATION; MECHANISM;

D O I：

10.1039/c5cc09468b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity of two nucleophilic palladiumcarbenes, [PC(sp(2))P]Pd(PMe3) and [PC(sp(2))P]Pd(PPh3), where [PC(sp(2))P] = bis[2-(di-iso-propylphosphino)phenyl]methylene, toward the E-H bond activation of Ph4-nEHn (E = Si, Ge; n = 1-3) and pinacolborane (HBpin) is discussed. Unlike previous reports, both types of isomer species, hydride [PC(EHn-1Ph4-n)P]PdH or [PC(Bpin)P]PdH and silyl/germyl [PC(H)P]-Pd(EHn-1Ph4-n), were observed depending on the substrate and the phosphine ligand, showing that the polarity of the Pd-C bond can be tuned by the phosphine substituents.

引用

页码：9048 / 9051

页数：4

共 36 条

[1]

[Anonymous], 1992, COMPREHENSIVE HDB HY, DOI DOI 10.1016/C2009-0-11185-6

[2] β-Elimination-Immune PCcarbeneP Iridium Complexes via Double C-H Activation: Ligand-Metal Cooperation in Hydrogen Activation [J].

Burford, Richard J. ;

Piers, Warren E. ;

Parvez, Masood .

ORGANOMETALLICS, 2012, 31 (08) :2949-2952

[3] A bis(thiophosphinoyl)methanediide palladium complex:: Coordinated dianion or nucleophilic carbene complex? [J].

Cantat, T ;

Mézailles, N ;

Ricard, L ;

Jean, Y ;

Le Floch, P .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (46) :6382-6385

[4] Palladium carbene complexes as persistent radicals [J].

Comanescu, C. C. ;

Vyushkova, M. ;

Iluc, V. M. .

CHEMICAL SCIENCE, 2015, 6 (08) :4570-4579

[5] C-H Activation Reactions of a Nucleophilic Palladium Carbene [J].

Comanescu, Cezar C. ;

Iluc, Vlad M. .

ORGANOMETALLICS, 2015, 34 (19) :4684-4692

[6] Synthesis and Reactivity of a Nucleophilic Palladium(II) Carbene [J].

Comanescu, Cezar C. ;

Iluc, Vlad M. .

ORGANOMETALLICS, 2014, 33 (21) :6059-6064

[7] Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products [J].

Corey, Joyce Y. .

CHEMICAL REVIEWS, 2011, 111 (02) :863-1071

[8] Reactions of hydrosilanes with transition-metal complexes: Formation of stable transition-metal silyl compounds [J].

Corey, JY ;

Braddock-Wilking, J .

CHEMICAL REVIEWS, 1999, 99 (01) :175-292

[9] Redox-induced umpolung of transition metal carbenes [J].

Cui, Peng ;

Iluc, Vlad M. .

CHEMICAL SCIENCE, 2015, 6 (12) :7343-7354

[10] Frustrated Lewis pair-like reactions of nucleophilic palladium carbenes with B(C6F5)3 [J].

Cui, Peng ;

Comanescu, Cezar C. ;

Iluc, Vlad M. .

CHEMICAL COMMUNICATIONS, 2015, 51 (28) :6206-6209

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