Monomeric and Dimeric Copper(II) Complexes of a Pyrrole‐Containing Tridentate Schiff‐Base Ligand

Li, Rongqing; Moubaraki, Boujemaa; Murray, Keith S.; Brooker, Sally

doi:10.1002/ejic.200900221

Cited by 22 publications

(5 citation statements)

References 26 publications

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“…In the previous work with a Zn(SNS) 2 hydroboration precatalyst, we also showed that the basic amido group binds strongly to the Bpin group, reducing the ligand’s ability to coordinate the metal . As a result, we turned to the less basic pyrrolyl group in L 2 . ,− …”

Section: Resultsmentioning

confidence: 92%

Comparing B–H Bond Activation in Ni^IIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Ataie

Baker

2022

Inorg. Chem.

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One of the key steps in many metal complex-catalyzed hydroboration reactions is B–H bond activation, which results in metal hydride formation. Anionic ligands that include multiple lone pairs of electrons, in cooperation with a metal center, have notable potential in redox-neutral B–H bond activation through metal–ligand cooperation. Herein, using an easily prepared NpyridineNimineNpyrrolide ligand (L2)−, a series of divalent NiIIX(NNN) complexes were synthesized, with X = bromide (2), phenoxide (3), thiophenoxide (4), 2,5-dimethylpyrrolide (5), diphenylphosphide (6), and phenyl (7). The complexes were characterized using 1H and 13C NMR spectroscopy, mass spectrometry, and X-ray crystallography and employed as precatalysts for nitrile dihydroboration. Superior activity of the phenoxy derivative (3) [vs thiophenoxy (4) or phenyl (7)] suggests that B–H bond activation occurs at the Ni–X (vs ligand Ni–Npyrrolide) bond. Furthermore, stoichiometric treatment of 2–7 with a nitrile showed no reaction, whereas stoichiometric reactions of 2–7 with pinacolborane (HBpin) gave the same Ni–H complex for 2, 3, and 5. Considering that only 2, 3, and 5 successfully catalyzed nitrile dihydroboration, we suggest that the catalytic cycle involves a conventional inner sphere pathway initiated by substrate insertion into Ni–H.

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Section: Resultsmentioning

confidence: 92%

Comparing B–H Bond Activation in Ni^IIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Ataie

Baker

2022

Inorg. Chem.

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“…The basal coordination sites are occupied by the three donor atoms of the Schiff-base ligand and the bromine atom Br(1) for 1 or one nitrogen atom [N(3) or N(8)] of the azide ligand for 2, while the apical position is occupied by the bromine atom [Br(1A)] for 1 or one nitrogen atom [N (10) or N(5A)] of the azide ligand of the next repeating unit. The apical Cu-Br(1A) (1) or Cu-N(azide) [Cu(1)-N(10), Cu(2)-N(5A)] (2) bond is significantly longer than the corresponding basal Cu-Br(1) (1) or Cu-N [Cu(1)-N(3), Cu(2)-N( 8)] (2) bond (Tables 2 and 3), a feature which appears frequently in square-pyramidal copper(II) complexes [23][24][25][26] . The copper atom is located 0.1682(15) Å for 1 or 0.1063(29) and 0.0828 (29) for 2 out of the basal plane towards the apical ligand.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Crystal Structures of One-Dimensional Chain Copper(II) Complexes of Two Phenol-Containing Schiff-Base Ligands

Zhang¹,

Li²,

Zhang³

et al. 2013

Asian J. Chem.

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Two copper(II) complexes of the tridentate Schiff-base ligands (L 1 )and (L 2 ) -, [CuL 1 (µ-Br)]∞ (1) and [CuL 2 (µ1,3-N3)]∞ (2), have been synthesized and characterized. The ligands [(L 1 )and (L 2 )are the deprotonated forms of 2-[(2-morpholin-4-ylethylimino)methyl]phenol (HL 1 ) and 2-[(2-piperidin-1-ylethylimino)methyl]phenol (HL 2 ), respectively]. X-Ray structure determinations carried out on complexes 1 and 2 reveal that both complexes are mono(µ-bromo)-bridged (for 1) or mono(µ1,3-azido)-bridged (for 2) square pyramidal copper(II) one-dimensional chain polymeric complexes.

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“…The synthesis of 1 – 5 is shown in Scheme . The tridentate pyrrole ligand C 4 H 3 NH(2‐CH=NCH 2 Py) was synthesized according to a method reported in the literature 7d. The reaction between 1 equiv.…”

Section: Results and Discussion Synthesis And Characterization Of 1–5mentioning

confidence: 99%

Aluminum Compounds Containing Pyrrole–Imine Ligand Systems – Synthesis, Characterization, Structure Elucidation, Ring‐Opening Polymerization, and Catalytic Meerwein–Ponndorf–Verley Reaction

Hsu

et al. 2014

Eur J Inorg Chem

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The reactions of AlMe3 with the tridentate pyrrole ligand precursor C4H3NH(2‐CH=NCH2Py) and subsequent treatment of the derivatives with small organic molecules such as 2,6‐diisopropylphenol or dibenzoylmethane were conveniently performed, and the products were characterized. The reaction between 1 equiv. of AlMe3 and 1 equiv. of a pyrrole–imine–pyridine ligand in toluene affords [Al{C4H3N(CHNCH2Py)Me2}] (1) in high yield. In addition, the use of 2 equiv. of AlMe3 with the same tridentate precursor results in the formation of a dialuminum compound [AlMe3{C4H3N(CHNCH2‐Py)AlMe2}] (2) in moderate yield. Furthermore, the combination of 1 with either 1 or 2 equiv. of 2,6‐diisopropylphenol or 2 equiv. of dibenzoylmethane in toluene yields aluminum monophenoxide or diphenoxide compounds [Al{C4H3N(CHNCH2‐Py)Me(O‐2,6‐iPr2C6H3)}] (3) and [Al{C4H3N(CHNCH2‐Py)}(O‐2,6‐iPr2C6H3)2] (4), respectively, as well as an aluminum bis‐diketonate compound, [Al{C4H3N(CHNCH2‐Py)}(PhCOCHCOPh)2] (5). All of the aforementioned derivatives were characterized by 1H and 13C NMR spectroscopy, and their solid‐state molecular structures were determined by single‐crystal X‐ray diffraction. The geometries of 1–5 show that the pyrrole ligand exists in the pyrrolyl–imine and azafulvene–amido resonance forms. Compounds 1, 3, 4 and 5 were used in the ring‐opening polymerization of ϵ‐caprolactone in the presence of BnOH and in the catalytic Meerwein–Ponndorf–Verley (MPV) reaction of 1‐naphthalenemethanol and 2‐naphthalenecarbaldehyde.

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Monomeric and Dimeric Copper(II) Complexes of a Pyrrole‐Containing Tridentate Schiff‐Base Ligand

Cited by 22 publications

References 26 publications

Comparing B–H Bond Activation in Ni^IIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Comparing B–H Bond Activation in Ni^IIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Synthesis and Crystal Structures of One-Dimensional Chain Copper(II) Complexes of Two Phenol-Containing Schiff-Base Ligands

Aluminum Compounds Containing Pyrrole–Imine Ligand Systems – Synthesis, Characterization, Structure Elucidation, Ring‐Opening Polymerization, and Catalytic Meerwein–Ponndorf–Verley Reaction

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Monomeric and Dimeric Copper(II) Complexes of a Pyrrole‐Containing Tridentate Schiff‐Base Ligand

Cited by 22 publications

References 26 publications

Comparing B–H Bond Activation in NiIIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Comparing B–H Bond Activation in NiIIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Synthesis and Crystal Structures of One-Dimensional Chain Copper(II) Complexes of Two Phenol-Containing Schiff-Base Ligands

Aluminum Compounds Containing Pyrrole–Imine Ligand Systems – Synthesis, Characterization, Structure Elucidation, Ring‐Opening Polymerization, and Catalytic Meerwein–Ponndorf–Verley Reaction

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Comparing B–H Bond Activation in Ni^IIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Comparing B–H Bond Activation in Ni^IIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)