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Synthesis, structure, and polymerization activity of cyclopentadienylnickel(II) N-heterocyclic carbene complexes: selective cross-metathesis in metal coordination spheres.
Autorzy
Rok wydania
2010
Czasopismo
European Journal of Inorganic Chemistry
Strony
648-656
DOI
10.1002/ejic.200900843
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The N‐heterocyclic carbene (NHC) complexes [(RC5H4)Ni(X)(NHC)] (2–5) have been prepared by treating nickelocene [or 1,1′‐bis(alkenyl)nickelocene] with a suitable carbene precursor. The alkenylcyclopentadienido complexes 4 and 5 undergo chemoselective cross‐metathesis with methyl acrylate or methyl vinyl ketone in the presence of the seocnd‐generation Grubbs catalyst to yield complexes 6–8, which bear an α,β‐unsaturated carbonyl substituent on the cyclopentadienido ligand. The X‐ray crystal structure of 2 [monoclinic,P21/n, Ni–Ccarbene 1.879(3) Å] and 7 [triclinic, P, Ni–Ccarbene 1.8874(6) Å] reveal undistorted trigonal‐planar Ni coordination. VT‐NMR studies of complexes 2 and 3, which possess an N‐alkyl substituent, show hindered rotation of the carbene ligand. Complexes [(RC5H4)Ni(X)(NHC)], in the presence of an excess of MAO, display high activity in the polymerization of styrene and moderate activity in the oligomerization of phenylacetylene.
Adres publiczny
https://doi.org/10.1002/ejic.200900843
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Podobne publikacje
N-heterocyclic carbene complexes of cyclopentadienylnickel(II): synthesis, structure and catalytic activity in styrene polymerization.
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