New Aspects of Recently Developed Rhodium(N‐Heterocyclic Carbene)‐Catalyzed Organic Transformations

Lee, Joo-Yeon; Hahm, Hyungwoo; Kwak, Jaesung; Kim, Min

doi:10.1002/adsc.201801085

Cited by 31 publications

(21 citation statements)

References 89 publications

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“…There is a surprising dearth of rhodium complexes with NHP +/ligands in the literature, as to the best of our FULL PAPER knowledge only one rhodium(I) NHP + complex has ever been crystallographically characterized, [26] and there is just one other report of compounds of this type. [27] This is especially perplexing considering the vast amount of attention NHC-bound rhodium(I) complexes have garnered in catalysis, [28][29][30] and the place of rhodium complexes in homogenous catalysis in general. [31] Herein, we describe the synthesis of a variety of PPP-ligated rhodium complexes, prepared through the isolation and reduction of the chlorophosphine precursor (PP Cl P)RhCl in a protocol similar to the synthesis of (PPP)CoPMe3.…”

Section: Introductionmentioning

confidence: 99%

N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand

et al. 2020

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The diphosphine, N-heterocyclic phosphenium (NHP + ) /phosphido (NHP -) containing ligand (PPP +/-) has been coordinated to rhodium to study the coordination chemistry of group 9 metals and NHP +/fragments. Addition of the chlorophosphine ligand PP Cl P to [Rh(COD)Cl]2 produces the complex (PP Cl P)RhCl ( 2), which can be reduced to form (PPP)RhPMePh2 (3), the asymmetric dimer [(PPP)Rh]2 (4) and the asymmetric dimer [(PPP)Rh(CN t Bu)]2 (5). Analysis of the solid-state structures and computational studies have provided insight into the electronic structure and bonding in 3-5, revealing that the NHP +/fragments in 3, 4 and 5 are best described using an NHP -/Rh I description. Both 3 and 5 were found to be reactive towards the S-H bond of thiophenol, generating (PPP)RhSPh ( 6) and (PPP)Rh(SPh)(CN t Bu) ( 7) respectively.

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Section: Introductionmentioning

confidence: 99%

N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand

et al. 2020

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“…The significance of N‐heterocyclic carbenes and of their anionic derivatives is impressively demonstrated by numerous books, monographs, and review articles, the latest of which reflect the broad applicability of this class of compounds. They deal with main group element adducts, NHCs in materials chemistry, NHCs as ligands in cross‐couplings and in rhodium‐catalyzed reactions as well as copper, nickel, and cobalt complexes . The enhancement of the σ‐donating properties of N‐heterocyclic carbenes was one of the initial goals of the design of a broad variety of interesting structures, resulting in strong donors such as cyclic alkyl amino carbenes (CAACs) and others.…”

Section: Introductionmentioning

confidence: 99%

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

et al. 2020

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Reaction of N-alkylated imidazoles with 2-chloro-4quinazolinone gave mesomeric betaines, 2-(1-alkyl-1H-imidazolium-3-yl)quinazolin-4-olates, for which three tautomeric forms of N-heterocyclic carbenes (NHCs) can be formulated, in addition to an anionic NHC after deprotonation. The NHC tautomers were trapped with sulfur, selenium, triethylborane, and triphenylborane as thiones, selenones and borane adducts, respectively. We obtained two isomers of the cyclic borane adducts, diazaboroloquinazolinones with [1,5-a] and [5,1-b]-type fusion between the quinazolinone and the diazaborole rings.[a] Scheme 3. Synthesis of the target betaines; 15 N-labeled atoms are marked in blue. Numbering. The index "b" stands for "mesomeric betaine". Scheme 4. Betaine, NHC tautomers and anionic NHC of 13. 452 stants (J C-N3 ) and by 1D 15 N NMR spectra (see Table S1 and Fig. S2, Supporting Information). The long-range 1 H-15 N couplings (J HN ) with 15 N labeled and unlabeled nitrogen atoms (at natural 15 Eur.

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“…If phosphines are usually thought as the most effective ligands in catalysis, carbene complexes with most metals are more stable than those obtained with analogous phosphines, with similar or even higher performances in a number of processes [47]. The variety of structures for the NHC ligands is clearly evident from the reports in the literature [48], with a few new entries.…”

Section: N-heterocyclic Carbene (Nhc) Ligandsmentioning

confidence: 99%

Rh(I) Complexes in Catalysis: A Five-Year Trend

et al. 2021

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Rhodium is one of the most used metals in catalysis both in laboratory reactions and industrial processes. Despite the extensive exploration on “classical” ligands carried out during the past decades in the field of rhodium-catalyzed reactions, such as phosphines, and other common types of ligands including N-heterocyclic carbenes, ferrocenes, cyclopentadienyl anion and pentamethylcyclopentadienyl derivatives, etc., there is still lively research activity on this topic, with considerable efforts being made toward the synthesis of new preformed rhodium catalysts that can be both efficient and selective. Although the “golden age” of homogeneous catalysis might seem over, there is still plenty of room for improvement, especially from the point of view of a more sustainable chemistry. In this review, temporally restricted to the analysis of literature during the past five years (2015–2020), the latest findings and trends in the synthesis and applications of Rh(I) complexes to catalysis will be presented. From the analysis of the most recent literature, it seems clear that rhodium-catalyzed processes still represent a stimulating challenge for the metalloorganic chemist that is far from being over.

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New Aspects of Recently Developed Rhodium(N‐Heterocyclic Carbene)‐Catalyzed Organic Transformations

Abstract: Scheme 11. Rh(NHC)-catalyzedb ishydroarylation of 2,2'-bipyridine derivatives.Scheme12. Rh(NHC)-catalyzedh ydroalkylation of 2-vinylpyridine.

Cited by 31 publications

References 89 publications

N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand

N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand

Betaine–N‐Heterocyclic Carbene Interconversions of Quinazolin‐4‐One Imidazolium Mesomeric Betaines. Sulfur, Selenium, and Borane Adduct Formation

Rh(I) Complexes in Catalysis: A Five-Year Trend

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