Synthesis and electrochemical activity of nickel phosphine complexes and polymers bound to electrode surfaces

Fox, Marye Anne; Chandler, Daniel A.; Wang, Pei Wei

doi:10.1021/ma00016a025

Cited by 8 publications

(4 citation statements)

References 2 publications

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“…The turnover number (TON) and the turnover frequency (TOF) are two important characters for catalytic reactions. The efficiency of catalysts are best represented by TON or TOF of the reaction. , The TON of nickel-catalyzed coupling reactions , is generally lower than that of palladium-catalyzed coupling reactions . In order to compare aryl neopentylglycolboronates with aryl pinacolboronates, the TON of cross-coupling of 4-methoxyphenyl neopentylglycolboronate and 4-methoxyphenyl pinacolboronate with methyl 4-((methylsulfonyl)oxy)benzoate were determined (Table ).…”

Section: Resultsmentioning

confidence: 99%

Comparison of Arylboron-Based Nucleophiles in Ni-Catalyzed Suzuki–Miyaura Cross-Coupling with Aryl Mesylates and Sulfamates

et al. 2012

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The efficiency of arylboron-based nucleophiles, boronic acid, potassium trifluoroborate, neopentylglycolboronate, and pinacol boronate in nickel-catalyzed Suzuki-Miyaura cross-coupling reactions with the two C-O electrophiles, mesylates, and sulfamates was compared. Arylboronic acid is the most reactive and most atom-economic of the four boron species studied. Arylpotassium trifluoroborate cross-couples efficiently only in the presence of water. In the absence of water, aryl neopentylglycolboronate is more efficient, less expensive, and more atom-economic than aryl pinacolboronate.

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Section: Resultsmentioning

confidence: 99%

Comparison of Arylboron-Based Nucleophiles in Ni-Catalyzed Suzuki–Miyaura Cross-Coupling with Aryl Mesylates and Sulfamates

et al. 2012

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“…A major problem in this field has been that, under the conditions commonly required for effective catalysis, ligand exchange reactions lead to leaching of the metal centers from the oxide-anchored ligands. The use of multidentate ligands functionalized with anchoring groups might limit this, but few such ligands have been described, probably because of synthetic difficulties …”

mentioning

confidence: 99%

Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

et al. 1997

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The ligand (Ph 2 P) 2 CdCH 2 (dppen) reacts with [RuCl 2 (PPh 3 ) 3 ] in CH 2 Cl 2 to give trans-[RuCl 2 (dppen) 2 ], 1. Complex 1 has reversible Ru(II)/Ru(III) electrochemistry, and on treatment with NOBF 4 , 1 affords [RuCl 2 (dppen) 2 ]BF 4 , 1 + . Refluxing solutions of 1 in chlorobenzene affords cis-[RuCl 2 (dppen) 2 ], 2. With excess RNH 2 in chlorobenzene or toluene, 1 reacts to give functionalized diphosphine complexes of general formula trans-principally by a small upfield shift in their 31 P{ 1 H} NMR spectra compared to that of 1 and by their distinctive 1 H NMR spectra. Complex 3b‚4MeOH crystallizes in the space group P1 h with a ) 11.448(6) Å, b ) 13.10(1) Å, c ) 11.178(7) Å, R ) 93.16(6)°, β ) 99.51(5)°, γ ) 92.19(5)°, V ) 1648(2) Å 3 , and D calcd ) 1.250 g cm -3 for Z ) 1. Complex 3e reacts with the surface hydroxyl groups of indium-doped tin oxide (ITO) electrodes, to give monolayers of anchored, redox-active Ru(II)-diphosphine complexes, characterized by cyclic voltammetry. The modified electrodes are stable to repetitive cycling over the Ru(II)/Ru(III) redox wave in acetonitriletetraethylammonium tetrafluoroborate and in aqueous buffer (pH 8). With anodized Pt electrodes, however, 3e reacts to form multilayers. Reaction of 1 with secondary amines is more sluggish than reaction with primary amines, and only adducts with pyrrolidine (3f) and morpholine (3g; impure) were isolated. With LiCtC(CH 2 ) 3 -CH 3 , 1 reacts to give trans-[Ru(CtCR) 2 ({Ph 2 P} 2 CHCH 2 CtCR) 2 ] (R ) n-butyl, 5); acetylide nucleophiles displace the chloride ligands as well as adding to the dppen double bonds of 1. Other carbanions fail to react with 1. The cis complex 2 reacts with a limited range of primary amines, to afford cis-[RuCl 2 ({Ph 2 P} 2 CHCH 2 NHR) 2 ] (R: n-hexyl, 4a; [CH 2 ] 3 Si[OEt] 3 , 4b). However, 4b was too insoluble for electrode derivatization. The "half-sandwich" complex [CpRuCl(dppen)] (6; Cp ) η 5 -C 5 H 5 ) also reacts with RNH 2 to give [CpRuCl({PPh 2 } 2 CHCH 2 NHR)] (R: -[CH 2 ] 3 NH 2 , 7a; -CH 2 Ph, 7b).

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“…Solutions of the ester 4 in chloroform-d 1 13 C resonances at 141.5 (m, AX 2 XЈ 2 , CH) and 135.5 (m, AXXЈXЉXٞ, CP). In the mass spectrum (EI) the molecular ion is observed at m/z 206 accompanied by fragment ions generated in the loss of hydrogen atoms.…”

Section: Preparation and Properties Of The Compoundsmentioning

confidence: 99%

Multifunctional Phosphorus Compounds: Molecular Structures of 1,2,4,5‐Tetra(phosphinyl)‐, Tetra(dimethoxyphosphoryl)‐, and Tetra(dihydroxyphosphoryl)benzene

Reiter

Nogai

Schmidbaur

2005

Zeitschrift anorg allge chemie

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1,2,4,5-Tetra(phosphinyl)benzene (1) and -tetrakis(dimethoxyphosphoryl)benzene (4) have molecular structures of point group C i symmetry with conformations largely determined by steric factors. In the crystal of compound 1 there are no discernible effects of intra-or intermolecular PϪH···P hydrogen bonding. By contrast, the crystal structure of the corresponding phosphonic acid, 1,2,4,5-tetrakis(dihydroxyphosphoryl)benzene (3), is governed by a network of hydrogen bonds between PO(OH) 2 groups with monofunctional PϪOH donors and difunctional PϭO acceptors as required for a maximum set of hydrogen bonds under the given stoichiometry. The aggregation of the molecules (C i symmetry) le-2595 ads to narrow channels formed by 14-and 16-membered rings which comprise POH···OP bridges between PϪCCϪP and PϪCCCϪP units, respectively. Accordingly, the crystals of compound 3 are mechanically extremely robust. A tri(phosphinyl)benzene (2) with an interesting 1,2,4-substitution pattern has been obtained as a by-product of the synthesis of the tetra(phosphinyl)benzene (1) where it is formed by reductive PϪC cleavage.

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Synthesis and electrochemical activity of nickel phosphine complexes and polymers bound to electrode surfaces

Cited by 8 publications

References 2 publications

Comparison of Arylboron-Based Nucleophiles in Ni-Catalyzed Suzuki–Miyaura Cross-Coupling with Aryl Mesylates and Sulfamates

Comparison of Arylboron-Based Nucleophiles in Ni-Catalyzed Suzuki–Miyaura Cross-Coupling with Aryl Mesylates and Sulfamates

Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

Multifunctional Phosphorus Compounds: Molecular Structures of 1,2,4,5‐Tetra(phosphinyl)‐, Tetra(dimethoxyphosphoryl)‐, and Tetra(dihydroxyphosphoryl)benzene

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Synthesis and electrochemical activity of nickel phosphine complexes and polymers bound to electrode surfaces

Cited by 8 publications

References 2 publications

Comparison of Arylboron-Based Nucleophiles in Ni-Catalyzed Suzuki–Miyaura Cross-Coupling with Aryl Mesylates and Sulfamates

Comparison of Arylboron-Based Nucleophiles in Ni-Catalyzed Suzuki–Miyaura Cross-Coupling with Aryl Mesylates and Sulfamates

Nucleophilic Addition to Complexes of (Ph2P)2CCH2as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes

Multifunctional Phosphorus Compounds: Molecular Structures of 1,2,4,5‐Tetra(phosphinyl)‐, Tetra(dimethoxyphosphoryl)‐, and Tetra(dihydroxyphosphoryl)benzene

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Nucleophilic Addition to Complexes of (Ph₂P)₂CCH₂as a Route to Functionalized, Redox-Active Ruthenium(II)−Diphosphine Complexes