13007-90-4Relevant academic research and scientific papers
Structural analogues of the bimetallic reaction center in acetyl CoA synthase: A Ni - Ni model with bound CO
Linck, Rachel C.,Spahn, Cameron W.,Rauchfuss, Thomas B.,Wilson, Scott R.
, p. 8700 - 8701 (2003)
Models for the active site of the acetyl CoA synthase (ACS) were synthesized by attachment of Cu+ and Ni(0) to nickel diaminodithiolate (S2N2) and diamidodithiolate (S2N2-) complexes. The Ni-Ni species form stable CO adducts, i.e., [{(CO)2Ni}{NiS2N2-}]2-, whereas the Cu-NiS2N2 and Cu-NiS2N2- models do not. These results provide supporting evidence for a biological role for reduced nickel in ACS. Copyright
Functionally substituted monocyclopentadienyl compounds. Formation of and derivatives with other phosphines. X-Ray crystal structure of
Ballester, L.,Perez, S.,Gutierrez, A.,Perpinan, M. F.,Gutierrez-Puebla, E.,et al.
, p. 411 - 420 (1991)
reacts with (X = Cl, Br, I, CN, SCN) to give monocyclopentadienyl complexes.The reactions of these complexes with tertiary phosphines or carbon monoxide are described.The crystal structure of has been determined, and shows the nickel atom to be in a pseudo-pentacoordinate environment.
Metal nitrosyls. III. The reaction of nitric oxide with nickel carbonyl
Feltham, Robert D.,Carriel, Jonathan T.
, p. 121 - 123 (1964)
The reaction of nitric oxide with nickel carbonyl in polar and nonpolar solvents leads to a variety of compounds derived from the species [NiNO]+. When this reaction is carried out in the presence of cyclopentadiene there is almost complete conversion to nitrosylcyclopentadienylnickel.
SYNTHESES OF ?-CYCLOBUT-1-EN-3-ONYL COMPLEXES BY CYCLOADDITION OF KETENES TO SOME TRANSITION METAL ALKYNYL COMPLEXES
Hong, Pangbu,Sonogashira, Kenkichi,Hagihara, Nobue
, p. 363 - 370 (1981)
Reactions of ketenes (R1R2C=C=O) with (η5-C5H5)Ni(PPh3)-CCR (1) and (η5-C5H5)Fe(CO)(L)-CCR (III, L = CO and PPh3) give ?-cyclobut-1-en-3-onyl complexes, (VI) and (IX)>, (2+2) cycloaddi
The reactivity of a nucleophilic nickel acylate complex
Hermanson, James R.,Figley, Timothy M.,Seibert, Anna L.,Pinhas, Allan R.
, p. 2061 - 2064 (2008)
The reactivity of a nucleophilic nickel acylate complex with a tungsten carbene complex, Fe(CO)5, Cr(CO)6, PPh3, and CO was investigated. With the tungsten carbene complex, a methyl transfer occurred. With the metal carbonyl complexes, the acylate group on the nickel and a carbonyl on the iron or chromium traded places. With the PPh3 and CO, the acylate anion was replaced by the phosphine or CO ligand.
Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides
Wang, Zhenhua,Wang, Xiu,Ura, Yasuyuki,Nishihara, Yasushi
supporting information, p. 6779 - 6784 (2019/08/26)
Ni-catalyzed decarbonylative cyanation of acyl chlorides with trimethylsilyl cyanide has been achieved. This transformation is applicable to the synthesis of an array of nitrile compounds bearing a wide range of functional groups under neutral conditions. The step-by-step experimental studies revealed that the reaction sequences of the present catalytic reaction are oxidative addition, transmetalation, decarbonylation, and reductive elimination.
Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel-Ketene Complexes
Staudaher, Nicholas D.,Arif, Atta M.,Louie, Janis
supporting information, p. 14083 - 14091 (2016/11/06)
A series of (dppf)Ni(ketene) complexes were synthesized and fully characterized. In the solid state, the complexes possess η2-(C,O) coordination of the ketene in an overall planar configuration. They display similar structure in solution, except in some cases, the η2-(C,C) coordination mode is also detected. A combination of kinetic analysis and DFT calculations reveals the complexes undergo thermal decomposition by isomerization from η2-(C,O) to η2-(C,C) followed by scission of the C=C bond, which is usually rate limiting and results in an intermediate carbonyl carbene complex. Subsequent rearrangement of the carbene ligand is rate limiting for electron poor and sterically large ketenes, and results in a carbonyl alkene complex. The alkene readily dissociates, affording alkenes and (dppf)Ni(CO)2. Computational modeling of the decarbonylation pathway with partial phosphine dissociation reveals the barrier is reduced significantly, explaining the instability of ketene complexes with monodentate phosphines.
Synthesis and reactions of mono- and dinuclear Ni(I) thiolate complexes
Ito, Mikinao,Matsumoto, Tsuyoshi,Tatsumi, Kazuyuki
, p. 2215 - 2223 (2009/08/08)
The dinuclear and mononuclear nickel(I) thiolates, [Ni(PPh 3)(μ-SR)]2 (1a: R is 2,4,6-triisopropylphenyl (Tip), 1b:R is 1-adamantyl (Ad)), (DxpS)Ni(μ-SDxp)Ni(PPh3)(2) (Dxp is 2,6-dixylylphenyl), and Ni(SDmp)(PPh3)(3) (Dmp is 2,6-dimesitylphenyl), have been synthesized by the reaction of the nickel(I) amide Ni{N(SiMe3)2}(PPh3)2 with the corresponding thiols. The two nickel centers of 1a and 1b are equivalent, and are linked by two thiolato sulfurs and aNi-Ni bond, whereas the two inequivalent nickels of 2 are connected by a SDxp sulfur, a η2/η 3-xylyl group of the other SDxp ligand, and a Ni-Ni bond. A slightly bulkier m-terphenyl thiolate, SDmp, prevents its nickel complex from forming a Ni-Ni bond, and the mononuclear nickel(I) center of 3 is bound to PPh 3 and SDmp through interactions with the sulfur and a η2-mesityl. The coordinatively unsaturated nickel(I) complex 3 is reactive, and the reaction of 3 with TEMPO generated diamagnetic Ni(SDmp)(PPh3)(O, N:η2-TEMPO) (4). N-Heterocyclic carbenes, 1,3,4,5-tetramethylimidazolin-2-ylidene (IMe′) and 1,3-bis-(2,4,6-trimethylphenyl)imidazolin-2-ylidene (IMes), also react with 3 to afford a dinuclear nickel(I) complex, [Ni(IMe′)(μ-SDmp)]2 (5), and a mononuclear nickel(I) complex, Ni(SDmp)(IMes) (6), respectively. The reaction of 3 with 1 equiv of tBuNC afforded the dinuclear complex [Ni(CNtBu)(μ-SDmp)]2 (7), whereas the analogous reaction with 1 equiv of CO resulted in a mixture of Ni(PPh3) 2(CO)2 and Ni(CO)(SDmp)2(PPh3)(8).
Synthetic, structural, and thermochemical studies of N-heterocyclic carbene (NHC) and tertiary phosphine ligands in the [(L)2Ni(CO)2] (L = PR3, NHC) system
Scott, Natalie M.,Clavier, Herve,Mahjoor, Parisa,Stevens, Edwin D.,Nolan, Steven P.
, p. 3181 - 3186 (2009/02/04)
Two new dicarbonyl N-heterocyclic carbene nickel(0) complexes of the type (NHC)2Ni(CO)2 (NHC = ICy, [N,N′- bis(cyclohexylimidazol)-2-ylidene (2), IMes [N,N′-bis(2,4,6- trimethylphenyl)imidazol)-2-ylidene] (3)) have been prepared by a substitution reaction of (NHC)Ni(CO)2 (NHC = ItBu [N,N′-bis(tert- butylimidazol)-2-ylidene], IAd [N,N′-bis(1-adamantylimidazol)-2-ylidene]) and 2 equivalents of ICy or IMes. Single-crystal X-ray analyses confirmed the monomeric 18-electron compositions of [(ICy)2Ni(CO)2] (2) and [(IMeS)2Ni(CO)2] (3). The greater electron-donating properties of the NHC ligands compared to tertiary phosphines are also demonstrated through calorimetric studies and enabled the determination of average bond dissociation enthalpies for Ni-L (L = NHC and tertiary phosphine).
Reaction of C(NMe2)4 with Ni(CO)4 - syntheses and structures of [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12], and[C(
Petz
, p. 2274 - 2280 (2008/10/08)
The reaction of C(NMe2)4 with Ni(CO)4 in THF produces the carbamoyl complex [C(NMe2)3][(CO)3NiC(O)-NMe2] (1); side products are the purple cluster compound [C(NMe2)su
