Binuclear Pd-methyl complexes of N,N′-{1, n}-alkanediyl-bis(pyridinyl-2-methanimine) ligands (n = 5, 8, 9, 10 and 12): Evaluation as catalysts precursors for phenylacetylene polymerization

Sibanyoni, J.M.; Bagihalli, Gangadhar B.; Mapolie, Selwyn F.

doi:10.1016/j.jorganchem.2011.11.019

Cited by 13 publications

(5 citation statements)

References 27 publications

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“…In summary, a series of new binuclear ionic sulfonated α‐diimine ligands were prepared and employed as ligands for palladium‐catalyzed Suzuki reactions. According to our results and recent work . both active sites in binuclear structure behave as an individual catalyst (like mononuclear) and completed the reaction more quickly than a mononuclear analogue.…”

Section: Resultssupporting

confidence: 85%

“…Thus transition metals with α‐diimines can adapt to a catalytic cycle containing an oxidative addition/reduction elimination sequence. Another advantage of this types of ligands is the facile tunability of their electronic and steric properties . There are several effective palladium catalysts which have α and β‐diimine skeletons used in Suzuki reactions .…”

Section: Introductionmentioning

confidence: 99%

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Effective binuclear Pd(II) complexes for Suzuki reactions in water

Hanhan

Cetinkaya

Shaver

2013

Applied Organom Chemis

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A series of new ionic binuclear Pd(II) complexes supported by water-soluble bis(α-diimine) ligands were prepared and employed as catalysts for the palladium-catalyzed Suzuki reaction in aqueous media. The binuclear nature of the complexes increased the reaction rate, while electronic and steric modification of the ligand frameworks had a remarkable influence upon the catalytic activity of the palladium complexes. The catalysts were shown to be homogeneous through mercury poisoning experiments and complexes could be recycled more than 10 times without loss of catalytic activity.

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Section: Resultssupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Effective binuclear Pd(II) complexes for Suzuki reactions in water

Hanhan

Cetinkaya

Shaver

2013

Applied Organom Chemis

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“…To the best of our knowledge, 2-t Bu is the most active phenylacetylene polymerization W-based catalyst, 28,29,[39][40][41][80][81][82][83][84][85][86][87][88][89] and more active than all known Mo-, [85][86][87][88][89][90] Rh-, 73,81,82,89,[91][92][93][94][95][96][97][98] Ir-, [98][99][100] and Pd-based catalysts. [101][102][103][104][105] Experiments were conducted to probe the mechanism of the acetylene polymerization by specically identifying the species that results from addition of one monomer unit to either 2-t Bu or 2-Ph. Unfortunately, adding 1 equiv.…”

Section: Polymerization Results: Monosubstituted and Disubstituted Ac...mentioning

confidence: 99%

Compelling mechanistic data and identification of the active species in tungsten-catalyzed alkyne polymerizations: conversion of a trianionic pincer into a new tetraanionic pincer-type ligand

et al. 2013

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Complex [ t BuOCO]W^C( t Bu)(THF) 2 (1) {where t BuOCO ¼ [2,6-( t BuC 6 H 3 O) 2 C 6 H 3 ] 3À , THF ¼ tetrahydrofuran} polymerizes acetylenes (R-phenylacetylene (R ¼ H, p-OMe, p-F, 3,5-diCF 3 ), 1-decyne, 3,3-dimethyl-1-butyne, and trimethylsilylacetylene) to form p-conjugating polymers. Upon treating 1 with 2 equiv. of phenylacetylene in toluene-d 8 at À35 C, two isolable products form. These two products are 4À } and derived from an apparent reductive alkylidyne migratory insertion into a metal-arene bond. Complexes 2-t Bu and 2-Ph polymerize acetylene and a wide variety of monosubstituted acetylenes including phenylacetylene derivatives, 1-decyne, 3,3-dimethyl-1-butyne and trimethylsilylacetylene. With a substrate to catalyst loading ratio of 25 000 : 1, complex 2-t Bu polymerizes phenylacetylene with a turnover number (TON) of 17 233. Additionally, 2-t Bu polymerizes phenylacetylene and 1-decyne with catalytic activities up to 5.64 Â 10 6 g PPA mol À1 h À1 and 7.98 Â 10 6 g PA mol À1 h À1 , respectively. 2-t Bu also polymerizes the disubstituted acetylene, 1-phenyl-1-propyne. NMR spectroscopic and single crystal X-ray structural studies provide compelling evidence for polymer chain growth via an insertion ring-expansion mechanism.

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“…The polymerization of phenyl acetylene produces stereoregular polyphenyl acetylene, which is known for its interesting properties like, conductivity, ferromagnetism and optical property [309] (Scheme 55). The nickel complexes (172−173), (175) and (182) were used in the polymerization of phenylacetylene [85].…”

Section: Phenylacetylene Polymerizationmentioning

confidence: 99%