15169-64-9Relevant academic research and scientific papers
Chlorobis(triphenylphosphine)-nickel(I) tetrahydrofuran solvate and an unsolvated trigonal phase of chlorotris(triphenylphosphine)-nickel(I)
Ellis, Dianne D.,Spek, Anthony L.
, p. 1067 - 1070 (2000)
In [NiCl(C18H15P)2]·C4H8O, the Ni atom is coordinated by three ligands in a distorted trigonal-planar configuration, with a P-Ni-P angle of 111.52 (2)°. In [NiCl(C18H15P)3], there are three independent molecules in the asymmetric unit, with each Ni-Cl bond on a crystallographic threefold rotation axis. Each Ni centre is tetrahedrally bound. The Ni atoms in both compounds have a d9 configuration and a formal oxidation state of NiI. A comparison is made between the form of [NiCl(PPh3)3] presented here and that of a known toluene solvate.
Field-Induced Slow Magnetic Relaxation in the Ni(I) Complexes [NiCl(PPh3)2]·C4H8O and [Ni(N(SiMe3)2)(PPh3)2]
Lin, Weiquan,Bodenstein, Tilmann,Mereacre, Valeriu,Fink, Karin,Eichh?fer, Andreas
, p. 2091 - 2100 (2016/03/19)
Direct current (dc) and alternating current (ac) magnetic measurements have been performed on the three Ni(I) complexes: [NiCl(PPh3)3], [NiCl(PPh3)2]·C4H8O, and [Ni(N(SiMe3)
Role of Radical Species in Salicylaldiminato Ni(II) Mediated Polymer Chain Growth: A Case Study for the Migratory Insertion Polymerization of Ethylene in the Presence of Methyl Methacrylate
?lscher, Franz,G?ttker-Schnetmann, Inigo,Monteil, Vincent,Mecking, Stefan
supporting information, p. 14819 - 14828 (2015/12/09)
To date, an inconclusive and partially contradictive picture exists on the behavior of neutral Ni(II) insertion polymerization catalysts toward methyl methacrylate (MMA). We shed light on this issue by a combination of comprehensive mechanistic NMR and EPR studies, isolation of a key Ni(I) intermediate, and pressure reactor studies with ethylene and MMA, followed by detailed polymer analysis. An interlocking mechanistic picture of an insertion and a free radical polymerization is revealed. Both polymerizations run simultaneously (25 bar ethylene, neat MMA, 70 °C); however, the chain growth cycles are independent of each other, and therefore exclusively a physical mixture of homo-PE and homo-PMMA is obtained. A Ni-C bond cleavage was excluded as a free radical source. Rather a homolytic P-C bond cleavage in the labile aryl phosphine ligand and the reaction of low-valent Ni(0/I) species with specific iodo substituted N^O (Ar-I) ligands were shown to initiate radical MMA polymerizations. Several reductive elimination decomposition pathways of catalyst precursor or active intermediates were shown to form low-valent Ni species. One of those pathways is a bimolecular reductive coupling via intermediate (N^O)Ni(I) formation. These intermediate Ni(I) species can be prevented from ultimate decomposition by capturing with organic radical sources, forming insertion polymerization active [(N^O)Ni(II)-R] species and prolonging the ethylene polymerization activity.
Tandem redox mediator/Ni(II) trihalide complex photocycle for hydrogen evolution from HCl
Hwang, Seung Jun,Powers, David C.,Maher, Andrew G.,Nocera, Daniel G.
, p. 917 - 922 (2015/02/05)
Photoactivation of M-X bonds is a challenge for photochemical HX splitting, particularly with first-row transition metal complexes because of short intrinsic excited state lifetimes. Herein, we report a tandem H2 photocycle based on combination of a non-basic photoredox phosphine mediator and nickel metal catalyst. Synthetic studies and time-resolved photochemical studies have revealed that phosphines serve as photochemical H-atom donors to Ni(II) trihalide complexes to deliver a Ni(I) centre. The H2 evolution catalytic cycle is closed by sequential disproportionation of Ni(I) to afford Ni(0) and Ni(II) and protolytic H2 evolution from the Ni(0) intermediate. The results of these investigations suggest that H2 photogeneration proceeds by two sequential catalytic cycles: a photoredox cycle catalyzed by phosphines and an H2-evolution cycle catalyzed by Ni complexes to circumvent challenges of photochemistry with first-row transition metal complexes.
Phosphino-indenyl complexes of nickel(II)
Groux, Laurent F.,Belanger-Gariepy, Francine,Zargarian, Davit
, p. 634 - 639 (2007/10/03)
The BH3-protected phosphinoindenyl ligand indenyl(CH 2)2PPh2·BH3 was used in the preparation of (η5/3:η0-indenyl(CH 2)2PPh2·BH3)Ni(PPh 3)Cl, which has been characterized by NMR spectroscopy and X-ray diffraction studies. On the other hand, all attempts at preparing the closely related complex (η5/3:η1indenyl(CH 2)2PPh2)NiCl, in which the tethered phosphine moiety is coordinated to the Ni centre, were unsuccessful. One of these unsuccessful attempts yielded instead the novel indenyl-PCP pincer complex {KP,KC,KP-1,3-(CH2CH 2PPh2)2-2-indenyl}NiCl, which has been characterized by X-ray diffraction studies.
Indenyl-nickel complexes bearing a pendant, hemilabile olefin ligand: Preparation, characterization, and catalytic activities
Gareau, Daniel,Sui-Seng, Christine,Groux, Laurent F.,Brisse, Francois,Zargarian, Davit
, p. 4003 - 4013 (2008/10/09)
The reaction of (PPh3)2NiCl2 with Li[Ind∧CH=CH2] gave the neutral complexes (η: η0-Ind∧CH=CH2)Ni(PPh3)Cl (Ind = indenyl; ∧ = (CH2)2, 1a; Si(Me)2CH 2, 1b), which were subjected to Cl- abstraction to give the corresponding cationic complexes [(η:η2-Ind∧CH= CH2)Ni(PPh3)]+ (∧ = (CH2) 2, 2a; Si(Me)2CH2, 2b). The bis(phosphine) derivatives [(η:η0-Ind-CH2CH2CH=CH 2)Ni(PPh3)2]+ (3a) and [(η3-allyl)Ni(PPh3)2]+ (4) formed gradually from room-temperature solutions of 2a and 2b, respectively, even in the absence of added PPh3. On the other hand, [(η:η0-Ind-SiMe2CH2CH=CH 2)Ni(PPh3)2]+ (3b) was detected only when PPh3 was added to a CD2Cl2 solution of 2b. The lability of the vinyl moiety in 2 allows these complexes to act as single-component precatalysts for the polymerization and hydrosilylation of styrene; the latter reaction requires little or no induction period with the hydrosilanes PhRSiH2 (R= Ph, Me, H) and proceeds with up to 1000 catalytic turnovers. Compounds 1a, 1b, 2a, 3a, and 4 have been characterized by NMR and single-crystal X-ray diffraction studies, whereas 2b and 3b were identified by NMR spectroscopy. Structural information gleaned from both solid-state and solution data provide important information on the Niolefin bonding in 2a and 2b and indicate that the Ni-Ind interactions in these complexes are affected by the significant trans influence of the chelating olefin moiety.
Chlorobis(triphenylphosphine)nickel(I)
Norman, Nicholas C.,Orpen, A. Guy,Quayle, Michael J.,Whittell, George R.
, p. m160-m161 (2007/10/03)
Crystals of the title compound, [NiCl(C18H15P)2], contain one molecule per asymmetric unit with no short intermolecular interactions. This is noteworthy since previous studies have reported that the formally 15-electron species oligomerizes in the solid state. The nickel(I) centre has a distorted trigonal-planar coordination geometry, the origin of which is suggested to be electronic in nature.
The Electro-Syntheses of Anhydrous Metal Chloride Complexes of Iron, Cobalt, and Nickel
Lehmkuhl, Herbert,Mehler, Klaus,Hauschild, Gerlinde
, p. 438 - 444 (2007/10/02)
The electro-syntheses of the anhydrous metal(II) chlorides od Fe, Co, and Ni are described.The appropriate metal is present in the form of a sacrificial anode and the reaction is carried out in an undivided cell with ethanolic solutions of hydrogen chloride.The primary products, MCl2 . n EtOH (1 - 3), are obtained in yields of 83 - 100percent based upon the current consumed and are converted into 4 - 6 upon reaction with THF, into 7 - 12 upon reaction with triorganophosphanes and into the tetrachlorometallate(II) complexes 13 - 15 upon reaction with Cl.Electrochemical reduction of nickel(II) chloride and triphenylphosphane (1 : 3) in THF leads to the formation of chlorotris(triphenylphosphane)nickel(I) (18) in 65percent yield.
Selective cis-Isomerization of 1-Pentene Catalyzed by Ni(I)-Triphenylphosphine Complexes
Kanai, Hiroyoshi,Kushi, Kenji,Sekanoue, Kei,Kishimoto, Nobuji
, p. 2711 - 2715 (2007/10/02)
Selective cis-isomerization of 1-pentene was carried out by NiX(PPh3)3 (X = halogen and pseudohalogen).First-order plots were obtained except for the iodo-complex.The addition of tin(II) chloride increased both activities and ratios of cis-2-pentene to the trans-isomer.Protic solvents accelerated the isomerization.Isotopic exchange between C2D4 and C2H4 or 1-pentene reveals that a metal hydride addition-elimination mechanism is operative.
