Development of Pincer Catalysts with Selected Group 8～10 Metals

Hao, Xin‐Qi; Niu, Jun‐Long; Zhao, Xuemei; Gong, Jun‐Fang; Song, Mao‐Ping

doi:10.6023/cjoc201301085

Cited by 24 publications

(5 citation statements)

References 14 publications

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“…Although the catalytic results are fairly good, the synthetic yield of this Pd(II) complex via C–H activation was rather low (<10%), which limited its further utilization in catalysis. As an extension of the applications of the chiral pincer Pd(II) catalysts, and also in continuation of our interests in the pincer metal complexes, herein we report our attempts to improve the yields of the Pd–Phebim complexes as well as their performance in the enantioselective hydrophosphination of enones with diphenylphosphine.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Hydrophosphination of Enones with Diphenylphosphine Catalyzed by Bis(imidazoline) NCN Pincer Palladium(II) Complexes

et al. 2014

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A series of chiral NCN pincer Pd(II) complexes with 1,3-bis(2′-imidazolinyl)phenyl (Phebim) ligands were synthesized via the C–H activation or oxidative addition method. A dinuclear macrocyclic Pd(II) complex was also prepared by reaction of the Phebim-H ligand with PdCl2. All of the new compounds were fully characterized, and X-ray single-crystal structures were obtained for two of the complexes. The Pd(II) complexes were successfully applied to enantioselective hydrophosphination of various enones with diphenylphosphine, providing optically active phosphine derivatives in good yields with enantioselectivities of up to 94% ee.

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Section: Introductionmentioning

confidence: 99%

Enantioselective Hydrophosphination of Enones with Diphenylphosphine Catalyzed by Bis(imidazoline) NCN Pincer Palladium(II) Complexes

et al. 2014

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“…Among them, the major work focused on NCN pincer complexes containing amine, imine, or various N-containing heterocycles as N donors. Because of our recent interest in the synthesis and applications of pincer metal complexes, , we developed NCN Pt(II) pincers containing 1,3-bis(2′-imidazolinyl)benzene ligands . These complexes were found to be luminescent in solution at room temperature, although the quantum yields were relatively low (0.0013–0.0018).…”

Section: Introductionmentioning

confidence: 99%

Neutral and Cationic NCN Pincer Platinum(II) Complexes with 1,3-Bis(benzimidazol-2′-yl)benzene Ligands: Synthesis, Structures, and Their Photophysical Properties

et al. 2014

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A series of neutral pincer Pt(II) chloride complexes 3–7 were first synthesized via the reaction of 1,3-bis(N-substituted benzimidazol-2′-yl) benzene (bzimb) ligands 2a–e with K2PtCl4 in refluxing HOAc. By treatment of complex 3 with KI and aromatic terminal alkynes in methanolic NaOH, the Pt(II) iodide complex 8 and Pt(II) acetylide complexes 9–11 were then obtained. Cationic Pt(II) complexes 12–15 were finally produced by the chloro-substitution reaction of complex 3 with AgOTf and several neutral N-donor ligands. With these new compounds in hand, various characterizations including elemental analysis, NMR, and IR were carried out to investigate their properties. On the basis of the X-ray single-crystal structure analysis of complexes 3–5, 8, 9, and 12, weak intermolecular interactions including π···π stacking and/or hydrogen bonds were found to be responsible for their assembly. After full investigation of the electronic absorption and photoluminescent properties of the Pt(II) complexes 3–15, time-dependent density functional theory (TD-DFT) calculations were carried out to elucidate the origins of the UV–vis absorptions. We were delighted to find that the luminescence quantum yields in degassed CH2Cl2 solution were around 0.13 in most cases and the emission lifetimes were in the microsecond range, indicating that these complexes could be used as bright phosphorescent materials with various potential applications in the future.

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“…Moreover, the C 2 -symmetric Rh–Phebim complexes consistently provided better enantioselectivities than the related C 2 - or C 1 -symmetric Rh–Phebox complexes in the addition of aromatic terminal alkynes to ethyl trifluoropyruvate under similar reaction conditions. Encouraged by the above results and also in continuation of our investigations of the pincer metal complexes, we decided to further determine the activity and stereocontrolling potential of the chiral pincer Rh–Phebim complexes. The highly enantioselective allylation of aldehydes and carbonyl–ene reaction of trifluoropyruvates using these complexes as the catalysts are described in this report.…”

Section: Introductionmentioning

confidence: 99%

Chiral Bis(imidazolinyl)phenyl NCN Pincer Rhodium(III) Catalysts for Enantioselective Allylation of Aldehydes and Carbonyl–Ene Reaction of Trifluoropyruvates

et al. 2013

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Chiral NCN pincer rhodium(III) complexes with bis(imidazolinyl)phenyl ligands were found to be effective catalysts for the allylation of a variety of electronically and structurally diverse aldehydes with allyltributyltin, giving the corresponding optically active homoallylic alcohols in high yields with enantioselectivities of up to 97% ee. These complexes were also applied in the carbonyl-ene reaction of ethyl or methyl trifluoropyruvate with various 2-arylpropenes. With the aid of silver trifluoromethanesulfonate, the pincer rhodium(III) catalysts could catalyze the reaction to provide the corresponding chiral α-hydroxy-α-trifluoromethyl esters in good yields with high stereoselectivities (up to 95% ee).

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Development of Pincer Catalysts with Selected Group 8～10 Metals

Cited by 24 publications

References 14 publications

Enantioselective Hydrophosphination of Enones with Diphenylphosphine Catalyzed by Bis(imidazoline) NCN Pincer Palladium(II) Complexes

Enantioselective Hydrophosphination of Enones with Diphenylphosphine Catalyzed by Bis(imidazoline) NCN Pincer Palladium(II) Complexes

Neutral and Cationic NCN Pincer Platinum(II) Complexes with 1,3-Bis(benzimidazol-2′-yl)benzene Ligands: Synthesis, Structures, and Their Photophysical Properties

Chiral Bis(imidazolinyl)phenyl NCN Pincer Rhodium(III) Catalysts for Enantioselective Allylation of Aldehydes and Carbonyl–Ene Reaction of Trifluoropyruvates

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