Kinetics and mechanism of ortho-palladation of ring-substituted NN-dimethylbenzylamines

DOI: 10.1039/DT9850002629

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2629 - 2638 (1985)

Update date:2022-08-03

Topics:

Authors:

Ryabov, Alexander D.

Sakodinskaya, Inna K.

Yatsimirsky, Anatoly K.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9850002629

Addition of excess of NN-dimethylbenzylamine to a chloroform solution of leads to instantaneous depolymerisation of the trimer giving the monomer trans-.Reversible dissociation of the amine from the latter affords a pseudothree-co-ordinate 14-electron intermediate which undergoes subsequent rate-limiting ortho-palladation to form the cyclopalladated acetato-bridged dimer <2>.The rate-limiting step is electrophilic in character; the slope ofthe corresponding Hammett plot for differently ring-substituted NN-dimethylbenzylamines is -1.6.The kinetic isotope effect, k_H/k_D', for PhCH2NMe2 is 2.2+/-0.2.The activation entropy for the ratelimiting step is very negative, ca. -250 J K^-1 mol^-1 for PhCH2NMe2, suggesting a highly ordered tight transition state.This dissociative path is a factor of ca. 100 faster than a parallel one, involving the 16-electron monomer trans- but without loss of the amine.Ortho-palladation is not rate-limiting in acetic acid solvent, where slow cleavage of acetate bridges in polynuclear palladium species occurs, affording a vacant co-ordination site for subsequent rapid ortho-palladation.A comparison of intra- and inter-molecular activations of carbon-hydrogen bonds in arenes by palladium(II) in terms of 'effective molarities' shows that the ratio k_intra/k_inter is not less than 3.6*10² mol dm^-3.

Full text of DOI:10.1039/DT9850002629

View Online / Journal Homepage / Table of Contents for this issue

View Online

Products guided by the article

Product name:diacetatobis{NN-dimethylbenzylamine-N}palladium(II)

Cas No:103903-69-1

R&D Labs maybe for 103903-69-1

Synochem Ingredients Corp., Ltd.

Contact:+86-512-5636 2180

Address:Zhangjiagang Free Trade Zone
Beijing Cooperate Pharmaceutical Co.,Ltd

website:http://www.cooperate-pharm.com/

Contact:86-01060279497

Address:No.507,Building 4,Tianhua Street, Biomedicine industrial Base
ANHUI WEICHI CHEMICAL CO.,LTD

website:http://www.weichichem.com

Contact:+8613912949432

Address:Fine Chemical Industrial Base,Wujiang town,He County,Anhui China.
Shanghai Micro-mega Industry Co., Ltd.

Contact:0086-21-34628682;57153848

Address:Rm413,No.413,West Meilong Road, Minhang District,Shanghai P R China
Haitong Chemical Industrial Co.,Ltd.

website:https://www.haitonglongwin.com/

Contact:+86-022-66221018

Address:18-701, No.99, The 4th Street, TEDA,

Relevant to this article

N-hydroxypyridine-2(1H)-thione derivatives of carboxylic acids as activated esters. Part I. The synthesis of carboxamides

Doi:10.1016/0040-4020(96)00487-5
(1996)
Monitoring differential changes of the mobility of cell membrane components following treatment with a tumor promoter by using pyrene and a novel fatty acid fluorophore.

Doi:10.1248/cpb.34.2161
(1986)
Bis-Benzimidazole-Appended Binucleating Porphyrin Ligands: Synthesis, Characterization, and X-ray Structure

Doi:10.1021/ja00282a020
(1986)
A convenient and stereoselective synthesis of 11Z-3,4-didehydroretinal by Horner-Emmons reaction using diphenyl phosphonate

Doi:10.1248/cpb.56.112
(2008)
Copolymerization of ethylene with 1-hexene promoted by novel multi-chelated non-metallocene complexes with imine bridged imidazole ligand

Doi:10.1002/pola.23800
(2010)
Thiated derivatives of 2',3'-dideoxy-3'-fluorothymidine: Synthesis, in vitro anti-HIV-1 activity and interaction with recombinant drug resistant HIV-1 reverse transcriptase forms

Doi:10.1016/j.antiviral.2011.05.012
(2011)

Article Doi