181709-83-1

Upstream product

• 1295-35-8 bis(1,5-cyclooctadiene)nickel ⁽⁰⁾ 
• 153625-67-3 1,2-bis-[(2,6-diisopropylphenyl)imino]acenaphthene 

Relevant academic research and scientific papers

Nickel complexes based on BIAN ligands: transformation and catalysis on ethylene polymerization

Treatment of bis(arylimino)acenaphthene (ArBIAN) with Ni(COD)2in toluene affordeddmpBIANNi(COD) (2a, dmp = 2,6-Me2C6H3) anddippBIANNi(COD) (2b, dipp = 2,6-iPrC6H3), respectively, in moderate yields. Complexes2aand2bcan be oxidized by a small amount of oxygen at low temperature leading to oxygen-bridged dinuclear Ni(ii) complexes (dmpBIANNi)2(μ-O)2(4a) and (dippBIANNi)2(μ-O)2(4b), respectively, as a purple powder. The reaction ofArBIAN with 0.5 equiv of Ni(COD)2or Ni(Ph3P)4gave bisligated complexes (dmpBIAN)2Ni (3a) and (dippBIAN)2Ni (3b), which can be considered as Ni(0) complexes supported by two neutral BIAN ligands. Oxidation of the bisligated nickel complexes3aand3bwith [Cp2Fe][B(C6F5)4] afforded cationic Ni(i) complexes [(dmpBIAN)2Ni][B(C6F5)4] (5a) and [(dippBIAN)2Ni][B(C6F5)4] (5b), respectively, in which the Ni(i) centre is chelated by two neutral Ar-BIAN ligands. These complexes were characterized by NMR and IR spectroscopy and DFT calculation, and the molecular structures of3b,4b, and5bwere well established by X-ray diffraction analysis. These complexes were evaluated as catalysts for ethylene polymerization in which2bshowed high activity in the presence of AlMe313C NMR analysis of polymers showed that the2b/AlMe3catalytic system gave less-branched polymers when compared to that obtained withdippBIANNiBr2under the same conditions.

Synthesis and exchange reactions of Ni-dimine-COD, acetylene and olefin complexes

The complexes MesDADNi(COD) (1), DippDADNi(COD) (2), DippDABNiCOD (3) and DippBIANNi(COD) (5) were readily prepared from Ni(COD)2. The analogous reaction of the ligand MesBIAN afforded (MesBIAN)2Ni (4). The related Ni alkyne complexes DADNi(PhCCPh) (6), DippDABNi(PhCCPh) (7) and DippBIANNi(PhCCPh) (8) are readily prepared by addition of alkyne to solutions of the COD species. The analogous reactions employing tBuDAD ligand with either Ni(COD)2 alone or Ni(COD)2 and PhCCPh led only to the known bis-ligand Ni complex, although tBuDADNi(MeCO2CCCO 2Me) (9) is readily prepared. In a similar fashion, the species DippDADNi(MeCO2CCCO2Me) (10), DippDABNi(Me 3SiCCSiMe3) (11), DippDABNi(MeCO2CCCO 2Me) (12) and DippBIANNi(MeCO2CCCO2Me) (13) were prepared. Reactions with olefins afforded DippDABNi(MeCO 2CHCHCO2Me) (14), DippDABNi(MeCO2CHCHPh) (15). Employing isolated (3) or (15) in exchange reactions afforded (7), (11) (14) and (15). Similarly (6) served as a precursor to (10) while (11) reacts with PhCCPh to give (7). The solid state structures of (1), (3)-(7), (9), (11) and (15) are reported. The Royal Society of Chemistry 2010.