2007
DOI: 10.1021/ja072218s
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Porphyrin Pincer Complexes:  Peripherally Cyclometalated Porphyrins and Their Catalytic Activities Controlled by Central Metals

Abstract: A series of heterobimetallic porphyrin pincer palladium complexes have been synthesized through direct cyclometalation of β,β‘-dipyridylporphyrin. X-ray analyses elucidated their highly distorted structures of porphyrin cores induced by the outer metalation. The catalytic activity has been investigated in the typical Heck reaction of iodobenzene with butyl acrylate. These complexes exhibit markedly different catalytic activities in the initial phase of the reaction, depending on the central metals.

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Cited by 103 publications
(59 citation statements)
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References 17 publications
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“…Stronger electronic interactions between the porphyrin and peripheral metal complexes are expected in the absence of orthogonal meso aryl groups. For example, the meso triarylporphyrin containing two pyridyl groups at the β‐pyrrolic positions adjacent to the free meso carbon (see Scheme ) provides an NCN pincer‐type ligand that was used for the synthesis of the corresponding Pd II complexes 2‐M (M=Zn II , Ni II , Cu II and 2H). When these complexes were used as pre‐catalysts in the Mizoroki‐Heck reaction between iodobenzene and butyl acrylate, the catalytic activity strongly depended on the nature of the inner metal ion and increased in the order 2‐2H < 2‐Cu II < 2‐Ni II < 2‐Zn II .…”
Section: Catalysis With Peripherally Metalated Porphyrinsmentioning
confidence: 99%
See 1 more Smart Citation
“…Stronger electronic interactions between the porphyrin and peripheral metal complexes are expected in the absence of orthogonal meso aryl groups. For example, the meso triarylporphyrin containing two pyridyl groups at the β‐pyrrolic positions adjacent to the free meso carbon (see Scheme ) provides an NCN pincer‐type ligand that was used for the synthesis of the corresponding Pd II complexes 2‐M (M=Zn II , Ni II , Cu II and 2H). When these complexes were used as pre‐catalysts in the Mizoroki‐Heck reaction between iodobenzene and butyl acrylate, the catalytic activity strongly depended on the nature of the inner metal ion and increased in the order 2‐2H < 2‐Cu II < 2‐Ni II < 2‐Zn II .…”
Section: Catalysis With Peripherally Metalated Porphyrinsmentioning
confidence: 99%
“…Strongere lectronic interactions between the porphyrin and peripheralm etal complexes are expected in the absence of orthogonal meso aryl groups. For example, the meso triarylporphyrin containing two pyridyl groups at the b-pyrrolic positions adjacent to the free meso carbon (see Scheme 2) [16] provides an NCN pincer-type ligand that was used for the synthesis of the corresponding Pd II complexes 2-M (M = Zn II ,N i II ,C u II and 2H). When these complexes were used as pre-catalysts in the Mizoroki-Heck reaction between iodobenzene andb utyl acrylate,t he catalytic activity strongly depended on the nature of the inner metal ion and increased in the order 2-2H < 2-Cu II < 2-Ni II < 2-Zn II .T his observation wasn ot discussed at that time but it was clear that the inner metal ion had as trong impact on the catalytic activity.I nterestingly,w hen pyridyl ligands were replaced by N-methyl imidazole, the apparent catalytic activity of complex 3 in the same reactionw as enhanced compared to that of 2-Ni II .…”
Section: Modulation Of the Electronic And Catalytic Propertiesmentioning
confidence: 99%
“…Metallacycles possessing the pincer ligand framework could be an efficient system because of their considerable thermal and oxidative stabilities [1][2][3][4][5][6][7][8][9]. Various types (e.g., PCP-, NCN-, CNC-) of pincer complexes of transition metals have been reported to date; among them, palladium-pincer complexes have been widely investigated and employed as catalysts for cross-coupling reactions [10][11][12][13][14][15]. Much less attention has been paid to the nickel-pincer complexes [16][17][18][19][20][21][22], although the use of nickel catalysts instead of palladium catalysts sometimes offers advantages, such as cost effectiveness and distinct catalytic abilities [23][24][25][26][27][28][29][30][31][32][33].…”
Section: Introductionmentioning
confidence: 99%
“…Representative examples synthesized through this method include ¢,¢-bis(acrylyl)-substituted porphyrins that can serve as an effective sensitizer in solar cells, 118,119 multi-porphyrin oligomers, 120,121 planar doubly 1,3-butadiyne-bridged diporphyrins, 122 heterocycle-bridged porphyrin rings, 123125 2-borylated corroles, 126 biscorrolebased stable singlet biradicals, 127,128 face-to-face dioxoisobacteriochlorin dimers, 129 porphyrin pincer complexes that exhibited catalytic activity in Heck reactions, 130 Ptpincer complexes that undergo tweezers-like molecular motions responding to the oxidation state of the incorporated Pt metal, 131 and © 2 coordinating Ru(II) complexes. 132 Recent remarkable examples are ¢,¢-doubly linked porphyrin belts with significant molecular curvatures 133 and ring forming porphyrin barrels, 134 both of which can capture C 60 efficiently.…”
mentioning
confidence: 99%