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- Title
Synthesis, Structures and Properties of Half-Sandwich Nickel(II) Complexes with Backbone-Modified NHC Ligands.
- Authors
Banach, Łukasz; Guńka, Piotr A.; Górska, Dominika; Podlewska, Maja; Zachara, Janusz; Buchowicz, Włodzimierz
- Abstract
A series of seven nickel complexes [Ni(5-C5H5)(X)(NHC)] (X = Cl or Br; NHC = N-heterocyclic carbene) containing backbone-modified NHC ligands was prepared by treatment of nickelocene with the corresponding NHC·HX salts or, in the case of complex 1h [Ni(5-C5H5)(Cl)(IMesO)] (IMesO = 4- oxo-1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene), by deprotection of the corresponding NHC ligand in complex 1g [Ni(5-C5H5)(Cl)(IMesOPiv)] [IMesOPiv = 4-(pivaloyloxy)- 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene]. Singlecrystal X-ray structures were determined for complexes 1d [Ni(5-C5H5)(Cl)(Bn2-bimy)] (Bn2-bimy = 1,3-dibenzylbenz-imidazolin-2-ylidene), 1g and 1h. The coordination spheres around the nickel atoms resemble those of d8 NiL4 squareplanar complexes, with Ni-C(Cp) bond length differentiation and C-C bond alternation in Cp ligands being taken into account. Desymmetrization of the five-membered heterocyclic ring and a tautomeric equilibrium were observed for complex 1h. All new complexes are efficient precatalysts in three C- C bond-forming reactions (polymerization of styrene, polymerization of methyl methacrylate, Suzuki-Miyaura crosscoupling).
- Subjects
NICKEL compounds; CARBENES; LIGAND exchange reactions; MOLECULAR structure of ligands; STYRENE derivatives
- Publication
European Journal of Inorganic Chemistry, 2015, Vol 2015, Issue 34, p5677
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201500993