Rhodium(I) complexes containing a bulky pyridinyl N-heterocyclic carbene ligand: Preparation and reactivity

Wang, Chaoyu; Liu, Yihong; Peng, Shei-Ming; Liu, Shiuh‐Tzung

doi:10.1016/j.jorganchem.2006.06.004

Cited by 41 publications

(19 citation statements)

References 48 publications

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“…The coordination geometry around the metal centre is approximately square planar, as observed in other structures of neutral NHC-Rh I complexes, [16] with the CC vectors of the norbornadiene carbon carbon double bonds perpendicular to the coordination plane. The observed minor distortion is attributed to the rigidity and the small bite angle of the nbd ligand.…”

Section: Preparation and Structure Of The Rhodium Complexessupporting

confidence: 67%

Chiral Oxazoline‐NHC Ligands with and without CR₂ Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

et al. 2009

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A series of bidentate oxazoline-NHC ligands has been synthesized in which the two heterocycles are connected by a CH 2 linker. The corresponding rhodium(I) complexes were prepared by direct deprotonation of the imidazolium halide salts followed by the addition of a solution of [Rh(nbd)Cl] 2 at low temperature. The cationic square planar rhodium complexes were generated by halide abstraction via addition of an excess of KPF 6 in a CH 2 Cl 2 /water solvent system. Alternatively, the deprotonation of the imidazolium hexafluorophosphates and reaction with [Rh(nbd)Cl] 2 directly gave the complex cations. These as well as oxazoline-NHC systems, in

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Section: Preparation and Structure Of The Rhodium Complexessupporting

confidence: 67%

Chiral Oxazoline‐NHC Ligands with and without CR₂ Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

et al. 2009

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“…After synthesis of the N-arylimidazoles 1-4, [15,16] quaternization with 2-(bromomethyl)pyridines was performed to obtain the imidazolium salts 5-8 in yields between 86 % and 99 % (Scheme 1). [10,12,13] Scheme 1. Synthesis of imidazolium bromides.…”

Section: Resultsmentioning

confidence: 99%

“…[10,12] [1-(2-Pyridyl)methylene-3-mesityl]imidazolium Bromide (5a): The product (1.11 g, 86 %) was obtained as a dark pink solid. [ …”

Section: General Synthesis Of Imidazolium Bromides 5-8: Compounds 1-4mentioning

confidence: 99%

“…[8][9][10][11] However, relatively few reports have been published concerning the substitution pattern of the picoline ring, especially on the position directly adjacent to the nitrogen. [12][13][14] As this position has the largest steric influence on the coordination properties of the secondary donor, we were interested to see the effects of introducing different groups. Here we present the synthesis and structural characterization of several N-picolyl-NHC ligands, as well as the synthesis of their silver(I) and palladium(0) complexes.…”

Section: Introductionmentioning

confidence: 99%

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Bulky Picolyl Substituted NHC Ligands and Their Pd⁰ Complexes

et al. 2010

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Heterobidentate N‐heterocyclic carbene‐picolyl ligands with various substitution patterns and their palladium(0) complexes have been synthesized in excellent yields via their corresponding silver(I) complexes. These complexes are among the first examples where substitution next to the coordinating nitrogen is evaluated systematically. The complexes have been studied by NMR and X‐ray diffraction, confirming their bidentate nature. The complexes are active precatalysts in the transfer semihydrogenation of alkynes to Z‐alkenes, with activity and selectivity depending on the picolyl substituent to a high degree. Selectivities as high as 92 % were observed.

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“…The coordination geometry around the metal center is approximately square planar as observed in other structures of neutral NHC-Rh I complexes, and the ligand is monodendate. [22] The distortion from an ideal square-planar coordination is due to the rigidity and the small bite angle of the nbd ligand. To minimize the steric hindrance, the imidazolyl ring is twisted by almost 90°out of the coordination plane.…”

Section: Synthesis and Structural Characterization Of The Rhodium(i) mentioning

confidence: 99%

A New Class of Modular Oxazoline‐NHC Ligands and Their Coordination Chemistry with Platinum Metals

et al. 2008

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A novel family of enantiomerically pure imidazolium salts [(NHC-Ox)H] + X -(2a-g) has been generated bearing an oxazoline unit and in which both heterocycles are connected by a (dimethyl)methylene bridge. Deprotonation of the imidazolium salt 2f and subsequent reaction of the resulting free carbene with [Rh(nbd)Cl] 2 (nbd = norbornadiene) afforded the neutral rhodium(I) complex [(NHC-Ox)Rh(nbd)Br] (3) in which the ligand was found to be monodentate. Bromide abstraction lead to the air-stable cationic complex [(NHC-Ox)-Rh(nbd)]PF 6 (4) with the expected bidentate coordination

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Rhodium(I) complexes containing a bulky pyridinyl N-heterocyclic carbene ligand: Preparation and reactivity

Cited by 41 publications

References 48 publications

Chiral Oxazoline‐NHC Ligands with and without CR₂ Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

Chiral Oxazoline‐NHC Ligands with and without CR₂ Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

Bulky Picolyl Substituted NHC Ligands and Their Pd⁰ Complexes

A New Class of Modular Oxazoline‐NHC Ligands and Their Coordination Chemistry with Platinum Metals

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Rhodium(I) complexes containing a bulky pyridinyl N-heterocyclic carbene ligand: Preparation and reactivity

Cited by 41 publications

References 48 publications

Chiral Oxazoline‐NHC Ligands with and without CR2 Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

Chiral Oxazoline‐NHC Ligands with and without CR2 Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

Bulky Picolyl Substituted NHC Ligands and Their Pd0 Complexes

A New Class of Modular Oxazoline‐NHC Ligands and Their Coordination Chemistry with Platinum Metals

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Chiral Oxazoline‐NHC Ligands with and without CR₂ Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

Chiral Oxazoline‐NHC Ligands with and without CR₂ Bridges: A Comparative Study in Rhodium Hydrosilylation Catalysis

Bulky Picolyl Substituted NHC Ligands and Their Pd⁰ Complexes