Facile synthesis of Pd(ii) and Ni(ii) pincer carbene complexes by the double C–H bond activation of a new hexahydropyrimidine-based bis(phosphine): catalysis of C

Facile synthesis of Pd(ii) and Ni(ii) pincer carbene complexes by the double C–H bond activation of a new hexahydropyrimidine-based bis(phosphine): catalysis of C–N couplings

Published:2019 Issue:21 Volume:48 Page:7203-7210
ISSN:1477-9226
Container-title:Dalton Transactions
language:en
Short-container-title:Dalton Trans.

Author:

Subramaniyan Vasudevan¹²³⁴^ORCID,Dutta Bidisa¹²³⁴,Govindaraj Anbarasu¹²³⁴,Mani Ganesan¹²³⁴^ORCID

Affiliation:

1. Department of Chemistry

2. Indian Institute of Technology Kharagpur

3. Kharagpur

4. India 721 302

Abstract

A new hexahydropyrimidine-based NHC proligand undergoes facile double C–H bond activation to give Pd(ii) and Ni(ii) NHC pincer cationic complexes. The Pd complex catalyzes C–N cross couplings very efficiently.

Funder

Department of Science and Technology, Ministry of Science and Technology

Publisher

Royal Society of Chemistry (RSC)

Subject

Inorganic Chemistry

Link

http://pubs.rsc.org/en/content/articlepdf/2019/DT/C8DT03413C

Reference94 articles.

1. Transition metal–carbon bonds. Part XLII. Complexes of nickel, palladium, platinum, rhodium and iridium with the tridentate ligand 2,6-bis[(di-t-butylphosphino)methyl]phenyl

2. The facile cyclometallation reaction of 1,3-BIS[(diphenyl-phosphino)methyl]benzene

3. The title compound 4 was synthesized from dipotassium 1,8‐anthracenedisulfonate (9) and potassium diphenylphosphide (Ph 2 PK). On reaction of 4 with nickel(II) chloride and bis‐(benzonitrile)palladium(II) chloride, cyclometallation of the C – H bond in anthracene 9‐position led to the square‐planar chelate complexes 11 and 13, respectively. In the case of the palladium complex 13, the cyclometallated structure was proved by X‐ray structure analysis. Treatment with aqueous potassium cyanide did not remove nickel from 11, but converted 11 into 12 by substitution of chloride with cyanide, demonstrating the high stability of these cyclometallated chelate complexes.