NDLI: Direct synthesis of cis-dihalido-bis(NHC) complex of nickel(II) and catalytic application in olefin addition polymerization : Effect of halogen co- ligands and density functional theory study

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Weng, Linhong Zhou, Sen Wang, Quanrui Zhang, Dao Li, Zhiming
Description	Author Affiliation: Zhang D ( Department of Chemistry, Fudan University, 220 Handan Road, Shanghai, 200433, People's Republic of China. daozhang@fudan.edu.cn)
Abstract	Two novel amine -containing N-heterocyclic carbene ligand precursors [H(1a–b)]Br have been prepared in good yield and fully characterized. Direct syntheses of cis- and trans-dihalido-bis(NHC) nickel complexes $[Ni(NHC)_{2}X_{2}]$ (X = Cl, Br) are reported. The solid structures of $trans-[Ni(1a–b)_{2}Br_{2}]$ (2a–b) and $cis-[Ni(1a)_{2}Cl_{2}]$ (3) were determined by single-crystal X-ray analysis and 3 was found to be the first example of cis-configuration coordination of monodentate NHC ligands to a metal center for dihalido-bis(NHC) nickel complexes. DFT calculations were conducted to determine the energy difference between cis- and trans-isomers of complexes 2a and 3 bearing bromide and chloride co- ligands . The $cis-[Ni(1a)_{2}Cl_{2}]$ (cis-3) is 1.77–1.55 kcal $mol^{−1}$ lower in energy than its trans-isomer in polar solvents including $CH_{2}Cl_{2}$ and THF, while the $trans-[Ni(1a)_{2}Br_{2}]$ (trans-2a) is more stable than the cis-isomer similarly in the gas phase. The cis nickel complex 3 with two coordinated monodentate NHCs was tested for olefin addition polymerization at standard conditions. It was found that cis-3 was inactive in ethylene polymerization but showed moderate catalytic activities (0.5–3.0 × $10^{6}$ g of PNB (mol of $Ni)^{−1}$ $h^{−1})$ in the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst.
ISSN	14779226
Issue Number	33
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-09-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Alkenes Chemistry Halogens Organometallic Compounds Quantum Theory Catalysis Crystallography, X-Ray Heterocyclic Compounds Ligands Methane Analogs & Derivatives Models, Molecular Molecular Structure Nickel Chemical Synthesis Polymerization Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in