3806-59-5Relevant articles and documents
The Ru(η6-naphthalene)(η4-1,5-cyclooctadiene)/acetonitrile system as a homogeneous catalytic precursor for the fast isomerization of 1,5-cyclooctadiene and 1-hexene
Pertici, Paolo,Barretta, Gloria Uccello,Burzagli, Fabrizio,Salvadori, Piero,Bennett, Martin A.
, p. 303 - 311 (1991)
1,5-Cyclooctadiene and 1-hexene undergo isomerization to 1,3-cyclooctadiene and (E)-/(Z)-2-hexene, respectively, with high turnover number in the presence of the complex Ru(η6-naphthalene)(η4-1,5-cyclooctadiene) and acetonitrile.This high catalytic activity is observed only using acetonitrile as co-catalyst.A possible reaction mechanism, based on results from an 1H and 2H NMR study of the isomerization, is presented.
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Yur'ev,V.P. et al.
, (1974)
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Synthesis and reactivity of a masked PSiP pincer supported nickel hydride
Suh, Hee-Won,Guard, Louise M.,Hazari, Nilay
supporting information, p. 37 - 43 (2015/02/19)
Tridentate PSiP pincer ligands featuring two phosphine donors and an anionic Si donor have attracted considerable attention in recent years. Here, we report the synthesis of the η3-cyclooctenyl complex, (PhPSiP)Ni(η3-cyclooctenyl) (1; PhPSiP = Si(Me)(2-PPh2-C6H4)2) through the reaction of Ni(COD)2 with PhPSiHP (PhPSiHP = HSi(Me)(2-PPh2-C6H4)2). We propose, that as a result of β-hydride elimination of 1,3-COD, 1 can act as a synthetic equivalent for (PhPSiP)NiH. The reaction of 1 with a variety of different reagents including another equivalent of PhPSiHP to form (PhPSiP)2Ni (2), 1,3-COD and H2, PPh3 to form the Ni(0) species (PhPSiHP)Ni(PPh3) (3) and 1,3-COD and 2,6-lutidine·HCl to generate (PhPSiP)NiCl (4), 1,3-COD and H2 are in agreement with this hypothesis. In addition, in the reaction of 1 with BH3·THF, (PhPSiP)Ni(κ2-BH4) (5) was observed but could not be isolated. This reaction presumably proceeds via (PhPSiP)NiH. This is supported by the observation that the reaction of (CyPSiP)NiH (CyPSiP = Si(Me)(2-PCy2-C6H4)2) with BH3·THF formed (CyPSiP)Ni(κ2-BH4) (6). Catalytic reactions such as alkene isomerization and CO2 reduction using 1 as precatalyst are also consistent with a nickel hydride being accessible. Compounds 1, 2 and 6 were characterized by X-ray crystallography.
Highly active and recyclable heterogeneous iridium pincer catalysts for transfer dehydrogenation of alkanes
Huang, Zheng,Brookhart, Maurice,Goldman, Alan S.,Kundu, Sabuj,Ray, Amlan,Scott, Susannah L.,Vicente, Brian C.
experimental part, p. 188 - 206 (2009/10/02)
Pincer-ligated iridium complexes have proven to be highly effective catalysts for the dehydrogenation and transfer-dehydrogenation of alkanes. Immobilization onto a solid support offers significant potential advantages in the application of such catalysts particularly with respect to catalyst separation and recycling. We describe three approaches toward such immobilization: (i) covalent attachment to a Merrifield resin, (ii) covalent bonding to silica via a pendant alkoxysilane group, and (iii) adsorption on γ-alumina (γ-Al2O3), through basic functional groups on the para-position of the pincer ligand. The simplest of these approaches, adsorption on γ-Al2O3, is also found to be the most effective, yielding catalysts that are robust, recyclable, and comparable to or even more active than the corresponding species in solution. Spectroscopic evidence (NMR, IR) and studies of catalytic activity support the hypothesis that binding occurs at the para-substituent and that this has only a relatively subtle and indirect influence on catalytic behavior.