Energetics of Migratory Insertion Reactions in Pd(II) Acyl Ethylene, Alkyl Ethylene, and Alkyl Carbonyl Complexes

Rix, Francis C.; Brookhart, Maurice

doi:10.1021/ja00108a034

Cited by 206 publications

(146 citation statements)

References 1 publication

(2 reference statements)

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“…[27,28,32,33] Consequently, these complexes can be expected to act as oligomerization catalysts for α-olefins. In terms of activity towards the polymerization of 2-norbornene, ligand-free systems [35,40,41] based on simple metal salts, for instance Pd II , Ni II , or Co II compounds, are presumably superior to the investigated catalysts, but lack the structural versatility of bis(phosphane) complexes, which potentially may be helpful in controlling olefin insertion processes.…”

Section: Resultsmentioning

confidence: 99%

“…[27,28] This is illustrated by the fact that, until recently, just a few examples of late transition metal catalyzed formation of high molecular weight poly(ethylene) were known. [29Ϫ31] However, it has since been demonstrated that Pd II -and Ni II -based systems with bulky diimine ligands are not only capable of producing high molecular weight poly(ethylene), but even poly(α-olefin)s. [32,33] This finding was attributed to a blocking of β-hydride elimination by the sterically demanding ligand system.…”

Section: Polymerizationmentioning

confidence: 99%

See 1 more Smart Citation

Electron-Poor Olefin Polymerization Catalysts Based on Semi-Fluorinated Bis(phosphane)s

Wursche

Debaerdemaeker

Klinga

et al. 2000

Eur. J. Inorg. Chem.

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Section: Resultsmentioning

confidence: 99%

Section: Polymerizationmentioning

confidence: 99%

Electron-Poor Olefin Polymerization Catalysts Based on Semi-Fluorinated Bis(phosphane)s

Wursche

Debaerdemaeker

Klinga

et al. 2000

Eur. J. Inorg. Chem.

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“…5 α-Diimines, also a class of polynitrogenated ligands, are commonly used in catalysis for the polymerization of olefins, being constituents of the so-called Brookhart catalysts. 6 Several research groups have replaced α-diimines for α-iminoketones in these catalysts with good results. crystallographic characterization of two azo-containing complexes, cis-bis [4-nitro-2-(4- This study led to some unusual findings, namely the great importance of intramolecular π-π interactions in the determination of the conformations of the complexes, as well as of the non-classical intermolecular H-bonding, which played a significant role in the crystalline arrangement of the solids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structural and spectroscopic studies of novel azo-containing N,O-bonded complexes in the α-Iminoketone and Azophenolate forms

Visentin¹,

Ferreira²,

Bordinhão³

et al. 2010

J. Braz. Chem. Soc.

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Este artigo descreve a síntese e a caracterização espectroscópica e estrutural por difratometria de raios X em monocristal de dois novos complexos contendo o grupamento azo, cis-bis[4-nitro-2-(4-nitrofenilazo)-fenolato-κN 1 ]bis(piridino-κN)cádmio(II), 1, e cis-bis[2-(4-fenilazofenilimino)-2H-acenafteno-1-ona]dicloromercúrio(II), 2. Embora os ligantes e os metais sejam diferentes, observa-se para os dois complexos uma coordenação do tipo N,O-bidentada ao átomo central. Em 1, a coordenação é feita por um átomo de N do grupo azo e por um átomo de O do grupo fenolato, enquanto em 2 a coordenação ocorre exclusivamente via átomos de O e N da α-iminocetona. Ambos os complexos exibem interações intramoleculares do tipo π-π, que exercem um importante papel na determinação de suas estruturas moleculares, além de também exibirem arranjos supramoleculares governados por ligações de hidrogênio não-clássicas. Em adição, a estrutura de 2 é a primeira relatada na literatura com um novo tipo de ligante, a azo-iminocetona, e também a primeira contendo mercúrio complexado a uma α-iminocetona. This article describes the synthesis and the spectroscopic and structural characterization of two novel azo-containing complexes, cis-bis[4-nitro-2-(4-nitrophenylazo)-phenolate-κN 1 ] bis(piridino-κN)cadmium(II), 1, and cis-bis[2-(4-phenylazo-phenylimino)-2H-acenaphthylen-1-one]dichloromercury(II), 2. In spite of the different metal centres, both complexes show an N,Obidentate complexation to the metal. In 1 the metal coordinates to an azo N and to a phenolate O atom, whereas in 2 the metal binds to an O and an N atom of the α-iminoketone. Both complexes show intramolecular π-π interactions, which play an important role in their molecular structures. In addition they also present non-classical H-bonding, which is crucial to their supramolecular arrangements. Moreover, 2 is the first case in the literature of a complex with a new class of ligand, an azoiminoketone, as well as the first case of an α-iminoketone Hg complex.

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“…11 Very recently Brookhart also succeeded in the in situ characterization of [Pd(C(O)Me)(phen)(C 2 H 4 )]BAr 4 and [Pd(Me)(phen)(CO)]BAr 4 , two believed key intermediates in the palladium(II) mediated CO/ethene copolymerization. 15 Boersma et al reported a sequential insertion of CO and norbornene, starting from the neutral methyl complex Pd(Me)X(bpy) (X ) I, Cl). 16,17 However, varying the anion with each step was required to accomplish this sequential insertion.…”

Section: Introductionmentioning

confidence: 99%

Stepwise Successive Insertion of Carbon Monoxide and Allenes into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(p-anisylimino)acenaphthene

Groen¹,

Elsevier²,

Vrieze³

et al. 1996

Organometallics

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Propadiene, 3-methyl-1,2-butadiene (DMA), and 2,4-dimethyl-2,3-pentadiene (TMA) reacted via migratory insertion with both neutral and ionic Pd(R)X(p-An-BIAN) (R = Me (1), C(O)Me (2); X = Cl (a), SO3CF3 (b)) complexes, containing the rigid nitrogen ligand bis(p-anisylimino)acenaphthene (p-An-BIAN), resulting in the novel and stable allylpalladium complexes Pd(η3-C3H4R)X(p-An-BIAN) (R = Me (3), C(O)Me (6)), Pd(η3-C5H8R)X(p-An-BIAN) (R = Me (4), C(O)Me (7)), and Pd(η3-C7H12R)X(p-An-BIAN) (R = Me (5), C(O)Me (8)), respectively (X = Cl (a), SO3CF3 (b)). The neutral complexes 6a and 7a reacted with carbon monoxide to form the acylpalladium complexes Pd(C(O)C3H4C(O)Me)Cl(p-An-BIAN) (9) and Pd(C(O)C5H8C(O)Me)Cl(p-An-BIAN) (10), respectively, while the analogous trifluoromethanesulfonate complexes 6b and 7b were completely inert toward CO. Complexes 9 and 10 reacted again with propadiene and DMA, respectively, to yield the allylpalladium complexes Pd(η3-C3H4C(O)C3H4C(O)Me)Cl(p-An-BIAN) (11) and Pd(η3-C5H8C(O)C5H8C(O)Me)Cl(p-An-BIAN) (12), respectively. Also insertion of norbornadiene in complex 10 was possible, yielding the ionic complex [Pd(C7H8C(O)C5H8C(O)Me)(p-An-BIAN)]Cl (13a), which reacted with AgSO3CF3 to give [Pd(C7H8C(O)C5H8C(O)Me)(p-An-BIAN)]SO3CF3 (13b). The novel complexes 9−12 are the first isolated and fully characterized complexes formed by successive insertion reactions of carbon monoxide and allenes, while 13a is the first isolated complex containing a metal-bonded ter-oligomer of carbon monoxide, an allene, and norbornadiene. The X-ray crystal structure of 7a has been determined and shows a distorted square pyramidal geometry in which the BIAN ligand is bonded to the palladium center in an unusual asymmetric fashion (Pd−N(1) = 2.144(7) Å; Pd−N(2) = 2.600(8) Å).

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Energetics of Migratory Insertion Reactions in Pd(II) Acyl Ethylene, Alkyl Ethylene, and Alkyl Carbonyl Complexes

Cited by 206 publications

References 1 publication

Electron-Poor Olefin Polymerization Catalysts Based on Semi-Fluorinated Bis(phosphane)s

Electron-Poor Olefin Polymerization Catalysts Based on Semi-Fluorinated Bis(phosphane)s

Synthesis, structural and spectroscopic studies of novel azo-containing N,O-bonded complexes in the α-Iminoketone and Azophenolate forms

Stepwise Successive Insertion of Carbon Monoxide and Allenes into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(p-anisylimino)acenaphthene

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