Oxidative additions to nickel(0): preparation and properties of a new series of arylnickel(II) complexes

Hidai, Masanobu; Kashiwagi, T.; Ikeuchi, Toshiya; Uchida, Yasuzo

doi:10.1016/s0022-328x(00)90208-0

Cited by 180 publications

(97 citation statements)

References 8 publications

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“…Accordingly, the title compound can be synthesized by addition of chlorobenzene to Ni(PPh 3 ) 4 . [19] A previously published synthesis prepared the latter by reduction of Ni(acac) 2 with alkylaluminum compounds. [20] The disad-vantage of this reaction is the moderate yield of 55% for the preparation of Ni(PPh 3 ) 4 and the sensitivity of the alkylaluminum compounds.…”

Section: Resultsmentioning

confidence: 99%

“…Selected bond lengths (Å ) and angles (°) for the structure of the nickel complex in comparison to the higher homologues and the results of a DFT calculation at the B3LYP/6Ϫ31G(d) level Pt [27] Pd [23] Ni DFT (Ni) precursor) proceeds with yields of about 60% and the second reaction step (oxidative addition) with about 71%. [19] Yellow crystals of the title compound were obtained by slowly adding hexane to a saturated solution of the complex in toluene. Surprisingly, the X-ray structure was not known up to now even though the X-ray structures of the higher congeners were determined some years ago.…”

Section: Scheme 2 Synthesis Of Trans-chloro(phenyl)bis(triphenylphosmentioning

confidence: 99%

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Structural Characterization and a New One‐Pot Synthesis of trans‐Chloro(phenyl)bis(triphenylphosphane)nickel(II)

2003

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Section: Resultsmentioning

confidence: 99%

Section: Scheme 2 Synthesis Of Trans-chloro(phenyl)bis(triphenylphosmentioning

confidence: 99%

Structural Characterization and a New One‐Pot Synthesis of trans‐Chloro(phenyl)bis(triphenylphosphane)nickel(II)

2003

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“…Moreover, it has already been reported that a substituent in the ortho-position to the C-Br bond stabilizes the formed 9,13,[15][16] Therefore, the lack of a -substituent in the P3AOT polymerization is a second reason for the decreased stability of the growing Ni-center in this case. However, in contrast to P3AT [13] , in which the polymerization completely failed when a reversed thiophene monomer (with substituent in meta-position) was used, a polymer is still formed, albeit in a non-controlled fashion.…”

Section: Proposed Polymerization Mechanismmentioning

confidence: 71%

Ni‐Catalyzed Polymerization of Poly(3‐alkoxythiophene)s

Bergh

Winter

Gerbaux

et al. 2010

Macro Chemistry & Physics

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The Ni-catalyzed polymerization of poly(3-alkoxythiophene)s (P3AOTs) was studied and compared with the controlled chain-growth polymerization of poly(3-alkylthiophene)s (P3ATs). By varying the ratio of the initial monomer concentration to the initiator concentration, no linear dependence of the molar mass was observed, revealing that the polymerization does not proceed via a controlled mechanism. This was also confirmed by analyzing the end-groups of the polymer with MALDI-TOF mass spectrometry. To acquire more information on the polymerization mechanism, the formation of the actual monomer and the polymerization reaction were studied into more detail. These experiments proved that the polymerization proceeds via a chain-growth mechanism, although not in a controlled way. a Supporting information for this article is available at the bottom of the article's abstract page, which can be accessed from the journal's homepage at http://www.macros.wiley-vch.de, or from the author.-2 - IntroductionPoly(3-alkylthiophene)s (P3ATs) are a class of conjugated polymers that has been intensively studied over the past decades. The discovery by McCullough and Yokozawa of the chain-growth polymerization mechanism of P3ATs has led to a renewed interest in the synthesis of these polymers.[1] This chain-growth mechanism is made possible by the 'ringwalking process' of the Ni-catalyst, whereby the Ni(0) species is transferred intramolecularly along a polymer chain to its end where it oxidatively inserts in the C-Br bond. [2] Due to this mechanism, all polymer chains are equipped with the same end-groups, being a bromine and a hydrogen atom (after quenching with acid). It also allows control of the molar mass by adjusting the feed ratio of the monomer to the Ni-catalyst, and the formation of block copolymers by successive monomer addition.[3]The versatility of the quasi-controlled chain-growth polycondensation has also been demonstrated by the use of other monomers, polymerized with Ni-as well as Pd-catalysts. In this way, polyfluorenes [4] , poly(para-phenylenes) [5] and polypyrroles [3d] have been successfully prepared.If the polythiophene backbone is substituted with an alkoxy instead of an alkyl side-chain, a polymer with different characteristics is obtained. Regioregular HT-coupled poly(3-alkoxythiophene)s (P3AOTs) are electronically different and show a significantly higher  max compared to P3ATs. [6] Their Faraday rotation is much larger (Verdet constant up to 3x10 6 T -1 m -1 ) [7] and their magnetic properties differ [8] . Although their properties are interesting, the polymerization behavior of P3AOTs has never been studied in detail.An important finding in this respect is that starting the polymerization of P3AOT with an otolyl nickel initiator complex results in polymers which mainly bear o-tolyl/hydrogen endgroups -as would be formed by a controlled chain-growth mechanism -but also otolyl/bromine and even small amounts of Br/Br, Br/H and H/H end-groups.[9] Although most -3 -polymers were equipped with the initiator u...

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“…To elucidate the catalytic mechanism, stoichiometric reactions were carried out using NiPhCl(PPh3)2 (3) 52) , which was prepared by the oxidative addition of chlorobenzene to Ni(PPh3)4 (Scheme 5). In the presence of CO2 (1 atm pressure), Mn powder, Et4NI, and PPh3, 3 afforded the carboxylated product (2k-Me) in 47 % yield after derivatization to the corresponding methyl ester.…”

Section: Carboxylation Of Aryl Chloridesmentioning

confidence: 99%

Transition Metal-catalyzed Fixation of Carbon Dioxide <i>via</i> Carbon–carbon Bond Formation

Fujihara

Tsuji

2016

J. Jpn. Petrol. Inst.

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Carbon dioxide (CO2) is a readily available carbon source, but the thermodynamic characteristics of CO2 limit its widespread use in chemical reactions. This review summarizes the transformation of CO2 via carbon _ carbon bond-forming reactions. Ni complexes catalyzed the carboxylation of less reactive aryl chlorides and double carboxylation of internal alkynes in the presence of suitable reducing agents such as Mn or Zn powders under 1 atm of CO2. Using Cu complexes as catalysts under CO2 atmosphere, hydrocarboxylation and silacarboxylation of alkynes proceeded efficiently using hydrosilanes and silylboranes, respectively, as the reagents.

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Oxidative additions to nickel(0): preparation and properties of a new series of arylnickel(II) complexes

Cited by 180 publications

References 8 publications

Structural Characterization and a New One‐Pot Synthesis of trans‐Chloro(phenyl)bis(triphenylphosphane)nickel(II)

Structural Characterization and a New One‐Pot Synthesis of trans‐Chloro(phenyl)bis(triphenylphosphane)nickel(II)

Ni‐Catalyzed Polymerization of Poly(3‐alkoxythiophene)s

Transition Metal-catalyzed Fixation of Carbon Dioxide <i>via</i> Carbon–carbon Bond Formation

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