Recent advances in metal catalysts with hybrid ligands

Zhang, Wen Hua; Chien, Sheau Wei; Hor, T. S. Andy

doi:10.1016/j.ccr.2011.05.018

Cited by 152 publications

(56 citation statements)

References 302 publications

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“…Hybrid ligands are di-or polydentate ligands with at least two different chemical donor functionalities that have the potential to act in cooperation or synergy [117]. Metal complexes with hybrid NHC ligands and their applications have been well reviewed [9,10,32,118,119].…”

Section: M(0) Carbonyl Complexes With Hybrid Nhc Ligandsmentioning

confidence: 99%

“…One effective strategy is to tailor-design carbene ligands that can stabilise these complexes without hampering their reactivities or redox facility. This can be accomplished through the use of hybrid carbenes [117,187,188] whereby the carbene donor is complemented by a range of other hemilabile donors in proximity so that these donors can act in tandem or synchrony. These donors can switch across a range of coordinative states depending on the need of the metal.…”

Section: Cr(v)-nhc Complexesmentioning

confidence: 99%

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N-heterocyclic carbene complexes of Group 6 metals

Wang

Mohamed

et al. 2015

Coordination Chemistry Reviews

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Section: M(0) Carbonyl Complexes With Hybrid Nhc Ligandsmentioning

confidence: 99%

Section: Cr(v)-nhc Complexesmentioning

confidence: 99%

N-heterocyclic carbene complexes of Group 6 metals

Wang

Mohamed

et al. 2015

Coordination Chemistry Reviews

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“…The attractive feature of pincer palladacycles is the possibility for fine-tuning the catalytic activity by varying the two side arms to modify the palladium environment, by changing the donor atoms and their substituents, providing the opportunity to alter hard/soft acid base properties, or by changing the ring size, giving rise to varying steric hindrance [12]. These factors provide the potential for hemilabile coordination of the donor ligand arms with the metal center, an important consideration in the design of pincer palladacycles [15][16][17]. This can lead to different physical and chemical properties of the donor ligand arms, resulting in preferential decoordination of one of the ligand arms, providing the opportunity to fine tune the catalytic activity of unsymmetrical pincer palladacycles [18][19][20][21].…”

Section: Figurementioning

confidence: 99%

The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study

et al. 2016

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A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH 2 )C 6 H 3 }], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C-H bond activation, and used, along with PCN and N'CN unsymmetrical pincer palladacycles previously synthesized by the authors, to determine the extent to which the trans influence is exhibited in unsymmetrical pincer palladacycles. The trans influence is quantified by analysis of structural changes in the X-ray crystal and density functional theory (DFT) optimized structures and a topological analysis of the electron density using quantum theory of atoms in molecules (QTAIM) to determine the strength of the Pd-donor atom interaction. It is found that the trans influence is controlled by the nature of the donor atom and although the substituents on the donor-ligand affect the Pd-donor atom interaction through the varied electronic and steric constraints, they do not influence the bonding of the ligand trans to it. The data indicate that the strength of the trans influence is P > S > N. Furthermore, the synthetic route to the family of SCN pincer palladacycles presented demonstrates the potential of late stage derivitization for the effective synthesis of ligands towards unsymmetrical pincer palladacycles.

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“…1,2 In particular, P,N ligands are of interest because of the presence of both soft phosphorus and hard nitrogen donor sites. 3 Of the various topologies, 4−7 1,3-P,N ligands have shown ample applicability in transition-metal-based catalysis (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

et al. 2017

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Highly stable iminophosphanes, obtained from alkylating nitriles and reaction of the resulting nitrilium ions with secondary phosphanes, were explored as tunable P-monodentate and 1,3-P,N bidentate ligands in rhodium complexes. X-ray crystal structures are reported for both κ1 and κ2 complexes with the counterion in one of them being an unusual anionic coordination polymer of silver triflate. The iminophosphane-based ruthenium(II)-catalyzed hydration of benzonitrile in 1,2-dimethoxyethane (180 °C, 3 h) and water (100 °C, 24 h) and under solvent free conditions (180 °C, 3 h) results in all cases in the selective formation of benzamide with yields of up to 96%, thereby outperforming by far the reactions in which the common 2-pyridyldiphenylphosphane is used as the 1,3-P,N ligand.

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Recent advances in metal catalysts with hybrid ligands

Cited by 152 publications

References 302 publications

N-heterocyclic carbene complexes of Group 6 metals

N-heterocyclic carbene complexes of Group 6 metals

The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study

Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

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