Complexes with Poly(N-heterocyclic carbene) Ligands: Structural Features and Catalytic Applications

Poyatos, Macarena; Mata, José A.; Peris, Eduardo

doi:10.1021/cr800501s

Cited by 817 publications

(372 citation statements)

References 278 publications

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“…6,7,23 In line with preceding work using palladium, 11 this time averaged symmetry is fully retained on cooling to 185 K (see Figure S10). High symmetry is also adopted in a solid-state X-ray structure of 1a obtained using single crystals grown from diethylether -hexane under an inert atmosphere (Figure 1, left).…”

Section: Characterisationsupporting

confidence: 84%

“…3,4,5 Alongside the ever-growing interest in N-heterocyclic carbene (NHC) ligands, CCC and CNC pincer architectures featuring trans-NHC donors have been prepared and partnered with a wide variety of transition elements. 6 Palladium(II) based CCC and CNC complexes have been shown to be catalytically active in C-C coupling reactions and recently, inspired by work using PCP ligands, Chianese and co-workers have used analogous NHC-based variants in iridium-catalyzed alkane dehydrogenation reactions (e.g. C).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Reactivity of NHC-Based Rhodium Macrocycles

Andrew

Chaplin

2014

Inorg. Chem.

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Using a general synthetic procedure employing readily accessed terminal alkene functionalised pro-ligands and macrocyclisation by ring-closing olefin metathesis, rhodium carbonyl complexes have been prepared that contain lutidine-(1a; n = 1) and pyridine-(1b; n = 0) derived tridentate CNC macrocycles with dodecamethylene spacers. In solution 1a shows temperature invariant time averaged C 2 symmetry by 1 H NMR spectroscopy (CD 2 Cl 2 , 500 MHz), while in the solid-state two polymorphs can be obtained showing different conformations of the alkyl spacer about the metal-carbonyl bond (asymmetric and symmetric). In contrast, time-averaged motion of alkyl spacer in 1b can be halted by cooling below 225 K (CD 2 Cl 2 , 500 MHz) and the complex crystallises as a dimer with an interesting unsupported Rh···Rh bonding interaction (3.2758(6) Å). Oxidative addition reactions of 1a and 1b, using MeI and PhICl 2 , have been studied in situ by 1 H NMR spectroscopy, although pure Rh(III) adducts can ultimately only be isolated with the pyridine-based macrocyclic ligand. The lutidine backbone of 1a can be deprotonated by addition of K[N(SiMe 3 ) 2 ] and the resulting neutral dearomatised complex (5) has been fully characterised in solution, by variable temperature 1 H NMR spectroscopy, and in the solid-state, by X-ray diffraction.

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Section: Characterisationsupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of NHC-Based Rhodium Macrocycles

Andrew

Chaplin

2014

Inorg. Chem.

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“…1,2 Because of the chelate effect these bis-NHCs lead to metal complexes with higher stability compared to their monodentate (bis-)NHC counterparts ( Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

“…13,14 We are interested in the properties and reactivity of low-valent late transition metal complexes, notably electron rich zero-valent palladium NHC complexes, as these often play a vital role in the catalytic cycles of many reactions. [15][16][17][18] Although a lot of research has been devoted to bis-carbene Pd II (halide) 2 complexes, usually obtained by treating a bisimidazolium salt with Pd(OAc) 2 at elevated temperatures, 7,[19][20][21][22][23] we are not aware of any previous reports on chelate [ …”

Section: Introductionmentioning

confidence: 99%

Synthesis of palladium(0) and -(ii) complexes with chelating bis(N-heterocyclic carbene) ligands and their application in semihydrogenation

et al. 2013

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A transmetallation route, using silver(I) precursors, to several zero-and di-valent palladium complexes with chelating bis(N-heterocyclic carbene) ligands bearing various N-substituents has been established.The resulting complexes have been characterized by NMR and mass spectroscopy. In addition, the structure of a representative compound, [Pd 0 (bis-(Mes)NHC)(η 2 -ma)] (3a), was confirmed by X-ray crystal structure determination. In contrast to the transfer semihydrogenation, in which only low activity was observed, complex 3a showed activity (TOF = 49 mol sub mol cat −1 h −1 ) and selectivity comparable to its monodentate counterparts in the semihydrogenation of 1-phenyl-1-propyne with molecular hydrogen.

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“…Maggini reviewed P,N-binucleating ligands in bimetallic complexes [80], Peris et al [81] reviewed complexes with (N-heterocyclic carbene) ligands while Gavrilova and Bosnich [78] established the principles of ligand design.…”

Section: Homobimetallic Catalysis For Organic Synthesismentioning

confidence: 99%

Recent developments in homobimetallic reagents and catalysts for organic synthesis

Shimeng

et al. 2011

Chin. Sci. Bull.

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Organometallics are a family of useful organic chemicals because they play important roles in organic synthesis as reagents and as catalysts. They can be classified according to the number of metals they contain. Bimetallic compounds are important organometallics and they are either homobimetallic or heterobimetallic depending on whether the two metals are the same or different. In this paper, we focus on homobimetallic compounds. Homobimetallic compounds are generally used as dianions to react with electrophiles in organic synthesis. Recently, homobimetallics have also been used as catalysts in organic reactions such as in asymmetric reactions. homobimetallics, reagent, catalyst, synthesis, application Citation:Wu W, Gu D L, Wang S M, et al. Recent developments in homobimetallic reagents and catalysts for organic synthesis.

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Complexes with Poly(N-heterocyclic carbene) Ligands: Structural Features and Catalytic Applications

Cited by 817 publications

References 278 publications

Synthesis and Reactivity of NHC-Based Rhodium Macrocycles

Synthesis and Reactivity of NHC-Based Rhodium Macrocycles

Synthesis of palladium(0) and -(ii) complexes with chelating bis(N-heterocyclic carbene) ligands and their application in semihydrogenation

Recent developments in homobimetallic reagents and catalysts for organic synthesis

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