Amido-pincer complexes of Cu(II): Synthesis, coordination chemistry and applications in catalysis

Taghvaee, Mahroo; Rodríguez-Álvarez, María J.; García‐Álvarez, Joaquín; Rı́o, Ignacio del; Lough, Alan J.; Gossage, Robert A.

doi:10.1016/j.jorganchem.2017.03.021

Cited by 15 publications

(17 citation statements)

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“…Our reasoning for the production of the materials described above stems from our long standing interest in both fundamental structural elucidation [7][8][9][10][42][43] and catalysis [8,13,17,[20][21][22][23] with azole-containing transition metal (TM) complexes. Divalent Co and Cu compounds are well-known precursors for selective olefin polymerisation, in some cases under Atom Transfer Radical Polymerisation (ATRP) conditions.…”

Section: Syntheses and Structural Aspectsmentioning

confidence: 99%

“…Nuclear Magnetic Resonance spectra ( 1 H: 400 MHz; 13 C{ 1 H}: 101 MHz; 19 F{ 1 H}: 376 MHz) were obtained from CDCl3 solutions on Bruker Avance II AC-400 spectrometer operating at 300K. Signals were calibrated based on solvent residual for 1 H (δH = 7.26 ppm: CHCl3) and central 13 C resonance (δC = 77.17 ppm: CDCl3). Proton and carbon assignments were made using a variety of 2D-NMR experiments (COSY, HSQC, HMBC).…”

Section: General Considerationsmentioning

confidence: 99%

“…1 H NMR: δH = 3.83 (t, J = 8.5 Hz, 2H), 4.52 (t, J = 8.5 Hz, 2H), 5.53 (s, 1H), 7.44 (d, J = 8.5 Hz, 1H), 7.65 (dd, J = 2.0, 8.5 Hz, 1H), 7.92 (d, J = 2.0 Hz, H), 9.94 (s, 1H). 13 (5.25).…”

Section: General Considerationsmentioning

confidence: 99%

“…[1][2][3][4][5][6] In this regard, our research interests are primarily focused on the use of azole heterocycles for a variety of topics within coordination chemistry. These areas include fundamental structural studies, [7][8][9][10] metal-mediated polymerization, [11] catalysts for selective C-C bond formation (e.g., Suzuki-Miyaura coupling), [12,13] and medicinal chemistry. [17] Recently, we have turned our attention to a class of azole metalbinding agents that we call Tohda's Ligands (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Divalent cobalt and copper coordination complexes of κ2-N, O-derivatives of (Z)-1-R-2-(2′-oxazolin-2′-yl)-eth-1-en-1-ates: Structure and reactivity patterns

May

Resanović

Chojnacka

et al. 2021

Inorganica Chimica Acta

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The synthesis and characterisation of a small library of Co and Cu derivatives (29 examples) incorporating the (Z)-1-R 1 -2-(4',4'-R 2 -2'-oxazolin-2'-yl)-eth-1-en-1-ate (L: R 1 = alkyl or aryl; R 2 = H or Me) skeleton is described. This work includes six new derivatives of "Tohda's Ligands". In the case where R 2 = H, solid-state stable Co(II) materials of formula Co(κ 2 -N,O-L)2 could, in some cases, be obtained following base-induced deprotonation of L+H and treatment with hydrated CoX2 salts. These complexes display redox induced solution decomposition behaviour giving Co(κ 2 -N,O-L)3 as one isolable product. Stable Cu(II) complexes could only be obtained in the case of for R 1 = Ph and R 2 = H. In the case of R 2 = Me, distorted tetrahedral Co(II) compounds (also Co(κ 2 -N,O-L)2) are obtained as above (twelve examples). Square planar derivatives of Cu(II), of similar stoichiometry, are likewise isolated (eleven new examples). In contrast to the R 2 = H reactions, all of these latter materials were found to be air-stable in solution or the solid phase. In total, 18 complexes have been characterised by single crystal X-ray diffraction. Molecular modelling (PM6(tm) and DFT) are also used to elucidate the molecular properties of selected complexes. Only a single Co complex (R 1 = t-butyl and R 2 = Me) of the library displays reversible one-electron redox properties.

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Section: Syntheses and Structural Aspectsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Divalent cobalt and copper coordination complexes of κ2-N, O-derivatives of (Z)-1-R-2-(2′-oxazolin-2′-yl)-eth-1-en-1-ates: Structure and reactivity patterns

May

Resanović

Chojnacka

et al. 2021

Inorganica Chimica Acta

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Section: General Considerationsmentioning

confidence: 99%

Divalent Cobalt and Copper Coordination Complexes of κ2-N, O-Derivatives of (Z)-1-R-2-(2’-oxazolin-2’-yl)-eth-1-en-1-ates: Structure and Reactivity Patterns

May¹,

Resanović²,

Chojnacka³

et al. 2019

Preprint

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The synthesis and characterisation of a small library of Co and Cu derivatives (29 examples) incorporating the (Z)-1-R1-2-(4’,4’-R2-2’-oxazolin-2’-yl)-eth-1-en-1-ate (L: R1 = alkyl or aryl; R2 = H or Me) skeleton is described. This work includes six new derivatives of “Tohda’s Ligands”. In the case where R2 = H, solid-state stable Co(II) materials of formula Co(κ2-N,O-L)2 could, in some cases, be obtained following base-induced deprotonation of L+H and treatment with hydrated CoX2 salts. These complexes display redox induced solution decomposition behaviour giving Co(κ2-N,O-L)3 as one isolable product. Stable Cu(II) complexes could only be obtained in the case of for R1 = Ph and R2 = H. In the case of R2 = Me, distorted tetrahedral Co(II) compounds (also Co(κ2-N,O-L)2) are obtained as above (twelve examples). Square planar derivatives of Cu(II), of similar stoichiometry, are likewise isolated (eleven new examples). In contrast to the R2 = H reactions, all of these latter materials were found to be air-stable in solution or the solid phase. In total, 18 complexes have been characterised by single crystal X-ray diffraction. Molecular modelling (PM6(tm) and DFT) are also used to elucidate the molecular properties of selected complexes. Only a single Co complex (R1 = t-butyl and R2 = Me) of the library displays reversible one-electron redox properties.<br>

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Copper‐Catalyzed Chemo‐ and Enantioselective Radical 1,2‐Carbophosphonylation of Styrenes

et al. 2023

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The copper-catalyzed enantioselective radical difunctionalization of alkenes from readily available alkyl halides and organophosphorus reagents possessing a PÀ H bond provides an appealing approach for the synthesis of α-chiral alkyl phosphorus compounds. The major challenge arises from the easy generation of a Pcentered radical from the PÀ H-type reagent and its facile addition to the terminal side of alkenes, leading to reverse chemoselectivity. We herein disclose a radical 1,2-carbophosphonylation of styrenes in a highly chemoand enantioselective manner. The key to the success lies in not only the implementation of dialkyl phosphites with a strong bond dissociation energy to promote the desired chemoselectivity but also the utilization of an anionic chiral N,N,N-ligand to forge the chiral C(sp 3 )À P bond. The developed Cu/N,N,N-ligand catalyst has enriched our library of single-electron transfer catalysts in the enantioselective radical transformations.

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Amido-pincer complexes of Cu(II): Synthesis, coordination chemistry and applications in catalysis

Cited by 15 publications

References 142 publications

Divalent cobalt and copper coordination complexes of κ2-N, O-derivatives of (Z)-1-R-2-(2′-oxazolin-2′-yl)-eth-1-en-1-ates: Structure and reactivity patterns

Divalent cobalt and copper coordination complexes of κ2-N, O-derivatives of (Z)-1-R-2-(2′-oxazolin-2′-yl)-eth-1-en-1-ates: Structure and reactivity patterns

Divalent Cobalt and Copper Coordination Complexes of κ2-N, O-Derivatives of (Z)-1-R-2-(2’-oxazolin-2’-yl)-eth-1-en-1-ates: Structure and Reactivity Patterns

Copper‐Catalyzed Chemo‐ and Enantioselective Radical 1,2‐Carbophosphonylation of Styrenes

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