2294-94-2Relevant articles and documents
Very large counteranion modulation of cationic metallocene polymerization activity and stereoregulation by a sterically congested (perfluoroaryl)fluoroaluminate
Chen,Stern,Marks
, p. 2582 - 2583 (1997)
-
Multifaceted chelating μ-(η3:η3-antifacial)-(cis-C4R2H2) coordination motif in binuclear complexes
Liu, Cham-Chuen,Chan, Michael C. W.,Lo, Po-Kam,Lau, Kai-Chung,Yiu, Shek-Man
supporting information, p. 11056 - 11059 (2016/09/19)
A novel μ-C4R2H2 core structure (formed by an unprecedented regioselective, redox-neutral C(sp2)-C(sp2) coupling process) in binuclear group 4 complexes displays adaptable coordination and accommodates different metal sizes, and is sufficiently robust to promote interesting catalytic reactivity at the bimetallic centers.
Activation of heteroallenes by coordinatively unsaturated nickel(II) alkyl complexes supported by the hydrotris(3-phenyl-5-methyl)pyrazolyl borate (TpPh,Me) ligand
Abubekerov, Mark,Eymann, Léonard Y. M.,Gianetti, Thomas L.,Arnold, John
, p. 14581 - 14590 (2016/10/03)
Activation of sulfur containing heteroallenes by nickel(ii) alkyl complexes supported by the bulky hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand is described. Exposure of TpPh,MeNiCH2Ph (1a) and TpPh,MeNiCH2Si(CH3)3 (1b) to CS2 resulted in formation of the insertion products TpPh,MeNi(η2-CS2)CH2Ph (2a) and TpPh,MeNi(η2-CS2)CH2Si(CH3)3 (2b) in moderate yields. Reaction of 1a and MeNCS produced two species in a 1:1 ratio, identified as TpPh,MeNi(η2-MeNC)CH2Ph (3) and TpPh,MeNi(η2-MeNCS)SCH2Ph (4). Isolation of the unexpected insertion product (3) prompted an investigation into the activity of 1a-b in the presence of isocyanides (i.e.tBuNC), which resulted in isolation of TpPh,MeNi(η2-tBuNC)CH2Ph (5a) and TpPh,MeNi(η2-tBuNC)CH2Si(CH3)3 (5b). Similarly, reaction of 1a with OCS led to the isolation of a rare example of a Ni(i) carbonyl species TpPh,MeNiCO (6). Alternatively, complex 6 was also formed by exposure of 1a-b to an atmosphere of CO. Isolation of the intermediate species (TpPh,MeNi(η2-CO)CH2TMS (7b) and TpPh,MeNi(CO)(C(O)R, (8a-b) with R = Ph, TMS)) shed light on the formation of such species.
Reduction of carbonyl to methylene: Organosilane-Ga(OTf)3 as an efficient reductant system
Surya Prakash,Do, Clement,Mathew, Thomas,Olah, George A.
experimental part, p. 507 - 511 (2012/01/04)
Direct carbonyl reduction to methylene has been achieved by mild reductant system obtained from the combination of organosilane and gallium (III) trifluoromethanesulfonate {Ga(OTf)3}, a water tolerant, recyclable, catalyst. Among a series of organosilanes studied, dimethylchlorosilane (Me 2SiHCl, DMCS) showed the highest efficiency. Both aromatic and aliphatic ketones were effectively reduced to the corresponding methylene products with high functional groups tolerance, under very mild conditions in a relatively short period of time with good to excellent yields. Graphical Abstract: [Figure not available: see fulltext.]
