Nickel(II) complexes of the type [RM(oxam)MR] (oxam: oxalamidinate, R=n-butyl, n-hexyl): the first binuclear n-alkyl nickel complexes

Stollenz, Michael; Rudolph, Manfred; Görls, Helmar; Walther, Dirk

doi:10.1016/j.jorganchem.2003.07.021

Cited by 11 publications

(3 citation statements)

References 29 publications

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“…Both the phosphorus substituents of the PCP ligand and the hybridization of the cyclometalated carbon atom have significant influence on the chemistry of these complexes. For instance, the PC sp3 P i -Pr ligand stabilizes the Ni−Bu derivative toward β-H elimination; in contrast, the Ni−Bu derivative is unstable with the PC sp3 P t -Bu system under the same conditions . Similarly, (PC sp3 P i -Pr )NiBr was found to be a better catalyst than its PC sp2 P i -Pr and PC sp3 P t- Bu analogues for Kumada coupling; studies are underway to determine the scope of this and other coupling reactions.…”

Section: Discussionmentioning

confidence: 99%

Preparation and Reactivities of PCP-Type Pincer Complexes of Nickel. Impact of Different Ligand Skeletons and Phosphine Substituents

2008

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Reaction of the diphosphine ligand i-Pr2P(CH2)5P(i-Pr)2 with NiBr2 at 110 °C gives a mixture of the 16-membered bimetallacycle {i-Pr2P(CH2)5P(i-Pr)2}2Ni2Br4, 1, and the pincer-type complex {(i-Pr2PCH2CH2)2CH}NiBr, 2; the latter can also be obtained by heating 1 in the presence of 4-(dimethylamino)pyridine or under vacuum. Complex 2 undergoes transmetalation with RMgCl or RLi to give {(i-Pr2PCH2CH2)2CH}NiR (R = Me (4), CCMe (5), Ph (6), n-Bu (7), and CCPh (8)); the phenylacetylide derivative 8 was also obtained from the reaction of PhCCH with 4, 5, or 7. The Ni−Me derivative 4 reacts with PhX (X = I, Br, Cl) to give the product of C−C coupling reaction (Ph−Me) and the Ni−X analogues of 2, and tests have shown that 2 is a competent catalytic precursor for the coupling of PhCl and MeMgCl. The available evidence suggests that this catalytic process does not involve Ni0 intermediates. Indeed, cyclic voltammetry measurements show that 2 can undergo two consecutive oxidations, and attempts to generate isolable high-valent species yielded the five-coordinate, 17-electron NiIII species {(i-Pr2PCH2CH2)2CH}NiX2, 9, from the reaction of 2 with FeX3 (X = Cl, Br). Characterization of all new complexes, including X-ray diffraction studies on single crystals of complexes 1−6 and 9, is described.

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Section: Discussionmentioning

confidence: 99%

Preparation and Reactivities of PCP-Type Pincer Complexes of Nickel. Impact of Different Ligand Skeletons and Phosphine Substituents

2008

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“…Some of them have proven to be active catalysts in a number of C-C-linking reactions [1][2][3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Bi- and trinuclear oxalamidinate complexes of palladium as catalysts in the copper-free Sonogashira reaction and in the Negishi reaction

Rau

Lamm

Görls

et al. 2004

Journal of Organometallic Chemistry

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“…In solution, however, dissociation of the nitrogen-donor ligand readily occurs and in the NMR spectra resonances are observed that are due to a b-agostic hydrogen interaction of the coordinated alkyl group [25]. In another recent report a remarkably stable dinuclear nickel(II)-hexyl complex has been reported; the compound does not show any agostic interactions, neither in the solid state nor in solution [27]. In another recent report a remarkably stable dinuclear nickel(II)-hexyl complex has been reported; the compound does not show any agostic interactions, neither in the solid state nor in solution [27].…”

Section: Nickel-alkene and Nickel-alkyl Complexesmentioning

confidence: 98%

Nickel

Bouwman¹

2006

The Handbook of Homogeneous Hydrogenation

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Nickelneous hydrogenation reaction. In this section, a brief overview will be provided of mononuclear nickel complexes, which have been reported to catalyze homogeneously the hydrogenation of various olefins. Many of the reported nickel-containing hydrogenation catalysts are of the Ziegler type (i.e., a nickel salt in combination with a reducing agent such as trialkylaluminum), and in many cases it is questionable whether the reported complexes yield really homogeneous hydrogenation catalysts or that the observed catalytic hydrogenation activity is due to formation of colloidal (heterogeneous) nickel particles [5]. Coordination Chemistry and Organometallic Aspects of Nickel Nickel-Hydride Complexes Nickel 94Scheme 5.1 Different modes of dihydrogen activation. (a) Oxidative addition, forming a metal dihydride species; (b) homolytic activation, forming two metal monohydride species; (c) heterolytic splitting, forming a metal hydride species and a proton.

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Nickel(II) complexes of the type [RM(oxam)MR] (oxam: oxalamidinate, R=n-butyl, n-hexyl): the first binuclear n-alkyl nickel complexes

Cited by 11 publications

References 29 publications

Preparation and Reactivities of PCP-Type Pincer Complexes of Nickel. Impact of Different Ligand Skeletons and Phosphine Substituents

Preparation and Reactivities of PCP-Type Pincer Complexes of Nickel. Impact of Different Ligand Skeletons and Phosphine Substituents

Bi- and trinuclear oxalamidinate complexes of palladium as catalysts in the copper-free Sonogashira reaction and in the Negishi reaction

Nickel

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