Cationic olefin Pd(II) complexes bearing α-iminoketone N,O-ligands: synthesis, intramolecular and interionic characterization and reactivity with olefins and alkynes

Binotti, Barbara; Carfagna, Carla; Foresti, Elisabetta; Macchioni, Alceo; Sabatino, Piera; Zuccaccia, Cristiano; Zuccaccia, Daniele

doi:10.1016/j.jorganchem.2003.11.020

Cited by 29 publications

(24 citation statements)

References 50 publications

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“…This means that the thermodynamic stabilization is the critical factor for these catalysts. The analogous compounds [Pd(h 1 ,h 2 -C 8 H 12 OMe)(2,2'-bipyridine)]X, [13] which bear the more basic bipy ligand, consistently afford a productivity that is higher than that observed with compounds 3 a and 2, while compounds with less electron-donating N,N [54] or N,O ligands [55] are only marginally or not active at all.…”

Section: Activitymentioning

confidence: 97%

The Effect of Counterion/Ligand Interplay on the Activity and Stereoselectivity of Palladium(II)–Diimine Catalysts for CO/p‐Methylstyrene Copolymerization

Binotti

Bellachioma

Cardaci

et al. 2007

Chemistry A European J

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The catalytic activity and stereoselectivity of complexes [Pd(eta(1),eta(2)-C(8)H(12)OMe)(Ar--N==C(R')--C(R')==N--Ar)]X in the copolymerization of CO and p-methylstyrene have been correlated with their interionic structure in solution and in the solid state, as determined by (19)F,(1)H-HOESY NMR spectroscopy and X-ray diffraction studies, respectively. The highest productivity is obtained with unhindered diimine ligands bearing electron-donating substituents and with the least coordinating counterion. Copolymers with a microstructure ranging from atactic to predominantly isotactic are obtained. The degree of isotacticity increases as the steric hindrance in the apical positions and the coordinating ability of the counterion increase. The counterion is located close to the diimine in both solution and the solid state but it moves toward the palladium as the steric hindrance in the apical positions decreases. When the latter is small the counterion competes with the substrate for apical coordination, and consequently it affects the productivity. In the case of ortho-dimethyl-substituted ligands the counterion is confined in the back, above the N==C(R')--C(R')==N moiety, and does not affect the productivity. However, it contributes to increasing the stereoregularity of the copolymer by making the aryl moieties more rigid. With R'=Me and Ar=o-Me(2)C(6)H(3) an ll of 81 % and 72 % was obtained with X(-)=CF(3)SO(3) (-) or BArF(-), respectively. The isotacticity of the copolymers produced by ortho-monosubstituted catalysts depends greatly on the counterion and ranges from 30 % to 59 % with X(-)=BArF(-) and X(-)=CF(3)SO(3) (-), respectively, with Ar=o-EtC(6)H(4) and R'=Me. Based on the interionic structural results, this effect can be explained by a greater reduction of the copolymerization rate of C(s)-symmetric isomers with respect to their C(2)-symmetric counterparts.

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Section: Activitymentioning

confidence: 97%

The Effect of Counterion/Ligand Interplay on the Activity and Stereoselectivity of Palladium(II)–Diimine Catalysts for CO/p‐Methylstyrene Copolymerization

Binotti

Bellachioma

Cardaci

et al. 2007

Chemistry A European J

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“…Coordination of a-diimine 2 to nickel(II) gives a catalyst that can polymerize norbornene [22]. Additionally, complexes containing a-iminoketones have been shown to polymerize olefins [23] and phenylacetylene [24]. A schematic representation of compounds 1-6 investigated in this study is shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and X-ray crystallographic characterization of substituted aryl imines

Kovach

Peralta

Brennessel

et al. 2011

Journal of Molecular Structure

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“…This can be used, for example, to show that an anion such as BF 4 is in close proximity to the ligands of the organometallic compound, as was carried out by Macchioni et al with a 19 F-1 H HOESY experiment [24]. This can be used, for example, to show that an anion such as BF 4 is in close proximity to the ligands of the organometallic compound, as was carried out by Macchioni et al with a 19 F-1 H HOESY experiment [24].…”

Section: Fig 114 Trans (Left) and Cis (Right) Interactionsmentioning

confidence: 97%

Nuclear Magnetic Resonance Spectroscopy in Homogeneous Hydrogenation Research

Vries¹,

Koen²

2006

The Handbook of Homogeneous Hydrogenation

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Cationic olefin Pd(II) complexes bearing α-iminoketone N,O-ligands: synthesis, intramolecular and interionic characterization and reactivity with olefins and alkynes

Cited by 29 publications

References 50 publications

The Effect of Counterion/Ligand Interplay on the Activity and Stereoselectivity of Palladium(II)–Diimine Catalysts for CO/p‐Methylstyrene Copolymerization

The Effect of Counterion/Ligand Interplay on the Activity and Stereoselectivity of Palladium(II)–Diimine Catalysts for CO/p‐Methylstyrene Copolymerization

Synthesis and X-ray crystallographic characterization of substituted aryl imines

Nuclear Magnetic Resonance Spectroscopy in Homogeneous Hydrogenation Research

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