New copper(<scp>i</scp>) complexes of bulky 5-substituted-2-iminopyrrolyl ligands as catalysts for azide–alkyne cycloaddition

Gomes, Pedro T.; Cruz, Tiago Carpinteiro; Lopes, Patrícia S.; Lemos, M.A.N.D.A.; Veiros, Luı́s F.

doi:10.1039/d3dt00617d

Dalton Trans.

2023

DOI: 10.1039/d3dt00617d

|View full text |Cite

New copper(i) complexes of bulky 5-substituted-2-iminopyrrolyl ligands as catalysts for azide–alkyne cycloaddition

Pedro T. Gomes

Tiago Carpinteiro Cruz

Patrícia S. Lopes

et al.

Abstract: Five dinuclear copper(I) complexes of the type [Cu{κN,κN’-5-R-NC4H2-2-C(H)=N(2,6-iPr2C6H3)}]2 (1a-e; R = 2,4,6-iPr3C6H2 (a), R = 2,6-Me2C6H3 (b), R = 3,5-(CF3)2C6H3 (c), R = 2,6-(MeO)2C6H2 (d), R = CPh3 (e)) were...

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2023

2024

Publication Types

Select...

Article3

Relationship

Self Cite2

Independent1

Authors

Journals

Cited by 3 publications

References 144 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

The role of 2‐iminopyrrolyl copper(I) complexes in the Reversible‐Deactivation Radical Polymerization of methyl methacrylate

de Matos,

Cruz,

Lemos

et al. 2023

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

The role of 2‐iminopyrrolyl copper(I) complexes in the Reversible‐Deactivation Radical Polymerization (RDRP) of methyl methacrylate (MMA) is described. Mononuclear 2‐iminopyrrolyl copper(I) complexes [Cu{κ2N,N′‐NC4H3‐2‐C(H)=NR′}Ln] 1–7 (R′ = C6H5, Ln = (PPh3)2 (1); R′ = 2,6‐Me2C6H3, Ln = (PPh3)2 (2); R′ = 2,6‐iPr2C6H3, Ln = (PPh3)2 (3); R′ = 4‐NMe2C6H4, Ln = (PPh3)2 (4); R′ = CH3, Ln = (PPh3)2 (5); R′ = CH3, Ln = (PMe3)2 (6); R′ = CH3, Ln = PiPr3 (7)) were synthesized by the reaction of the in situ prepared sodium salts of precursors HL1–5 with [Cu(NCMe)4]BF4 with the respective phosphines. In their absence, the binuclear complex [Cu{κN,κN'‐NC4H3‐2‐C(H)=NCH3}]2 8 was formed instead, which, when treated with one equivalent of PR3 yielded the binuclear complexes [Cu2{κN,κN'‐NC4H3‐2‐C(H)=NCH3}2PR3] 9 (R = Ph) and 10 (R = Me).All complexes, except 8, were active in the RDRP of MMA using the initiator tert‐butyl‐α‐bromoisobutyrate (tBiB‐Br), achieving apparent propagation kinetic constants (kp') in the range of 0.5–7.5 × 10−5 s−1, at 90 °C and with a [MMA]0:[complex]0:[tBiB‐Br]0 ratio of 500:1:1. All reactions yielded poly (methyl methacrylate)s with molecular weights () and dispersities higher than expected for Controlled Radical Polymerization processes. Complex 7 achieved the best results, with values being only 1.2‐fold higher than theoretically expected. Experimental and density functional theory (DFT) studies suggest that this system operates via Atom Transfer Radical Polymerization/Organometallic Mediated Radical Polymerization (ATRP/OMRP) mechanisms interplay.

show abstract

The role of 2‐iminopyrrolyl copper(I) complexes in the Reversible‐Deactivation Radical Polymerization of methyl methacrylate

de Matos,

Cruz,

Lemos

et al. 2023

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

show abstract

Hydroboration of aldehydes with pinacolborane catalyzed by bulky 2‐iminopyrrolyl copper(I) triphenylphosphine complexes

Cruz,

Figueira,

Gomes

2023

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

Eight new copper(I) triphenylphosphine complexes of bulky 5‐substituted‐2‐iminopyrrolyl ligands [Cu{κ2N,N′‐5‐R‐NC4H2–2‐C(H) = N(2,6‐iPr2C6H3)}(PPh3)n] (for n = 2: R = 2,6‐Me2C6H3 (1), 3,5‐(CF3)2C6H3 (2); for n = 1: R = 2,4,6‐iPr3C6H2 (3), CPh3 (4), 2,6‐(OMe)2C6H3 (5), 2,4,6‐Ph3C6H2 (6), 2,6‐Me2C6H3 (7), 3,5‐(CF3)2C6H3 (8)) are presently reported. The complexes were prepared in good yields by: (1) the reaction of the previously reported binuclear complexes [Cu{κN,κN'‐5‐R‐NC4H2‐2‐C(H) = N(2,6‐iPr2C6H3)}]2 (D1–D6) with triphenylphosphine (PPh3); (2) the reaction of the respective 5‐R‐2‐iminopyrrolyl potassium salts (KL1–KL3 and KL5) and [Cu(NCMe)2(PPh3)2]BF4; or (3) the abstraction of one PPh3 ligand present in complexes 1 and 2 with one equivalent of tris(pentafluorophenyl)borane (only for complexes 7 and 8, respectively). All complexes were characterized by NMR spectroscopy, elemental analysis and, in selected cases, by single crystal X‐ray diffraction. The single crystal X‐ray diffraction structures of 1, 3, and 5–7 displayed tetrahedral (for 1) and trigonal planar (for 3 and 5–7) coordination geometries. All complexes catalyzed the 1,4‐hydroboration of some α,β‐unsaturated (E)‐2‐enals with pinacolborane (HBPin), with 1,4:1,2‐addition selectivities as high as 29:1, the maximum turnover frequencies being equal to 9.9 min−1, and the 1,4‐hydroboration selectivity being favored by increasing steric protection of the 5‐substituted‐2‐iminopyrrolyl scaffold. Additionally, these complexes also catalyzed the hydroboration of an array of other aldehydes, reaching TOFs as high as 9.9 min−1. A combination of control experiments suggests that the catalyst system operates via a non‐classical copper‐hydride outer sphere route.

show abstract

Organoaluminum complexes containing a pyrrolylaldiminate pincer ligand

Lin,

Cheng

et al. 2024

Polyhedron

View full text Add to dashboard Cite

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

hi@scite.ai

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

New copper(i) complexes of bulky 5-substituted-2-iminopyrrolyl ligands as catalysts for azide–alkyne cycloaddition

Abstract: Five dinuclear copper(I) complexes of the type [Cu{κN,κN’-5-R-NC4H2-2-C(H)=N(2,6-iPr2C6H3)}]2 (1a-e; R = 2,4,6-iPr3C6H2 (a), R = 2,6-Me2C6H3 (b), R = 3,5-(CF3)2C6H3 (c), R = 2,6-(MeO)2C6H2 (d), R = CPh3 (e)) were...

Cited by 3 publications

References 144 publications

The role of 2‐iminopyrrolyl copper(I) complexes in the Reversible‐Deactivation Radical Polymerization of methyl methacrylate

The role of 2‐iminopyrrolyl copper(I) complexes in the Reversible‐Deactivation Radical Polymerization of methyl methacrylate

Hydroboration of aldehydes with pinacolborane catalyzed by bulky 2‐iminopyrrolyl copper(I) triphenylphosphine complexes

Organoaluminum complexes containing a pyrrolylaldiminate pincer ligand

Contact Info

Product

Resources

About