Synthesis and characterization of two dioxidomolybdenum(VI) complexes bearing amidinato and pyrazolato ligands and their use in thin film growth and oxygen atom transfer reactions

El‐Kadri, Oussama M.; Siddique, Ameer A.; Eaton, Michael; Nath, N.

doi:10.1016/j.poly.2018.03.009

Cited by 3 publications

(2 citation statements)

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“…Interestingly, two new signals at δ 28.0 and δ 21.5 (Ph 3 PO) were found in the catalysis by 31 P NMR analysis, and the former signal was thought to be the active intermediate. To trap the new compound, we performed an experiment with Ph–NO 2 (1 equiv), W(CO) 6 (1 equiv), and PPh 3 (3 equiv) under 365 nm LED irradiation for 24 h at ambient temperature (Scheme c).…”

Section: Resultsmentioning

confidence: 97%

“…Interestingly, two new signals at δ 28.0 and δ 21.5 (Ph 3 P O) 18 were found in the catalysis by 31 Furthermore, judging from the 31 P NMR analysis, cis-W is not stable at 25 °C and will smoothly convert to trans-W (see Figure S9 for more details). The mixture of the isomers reached an equilibrium state of cis-W/trans-W = 0.55:1 after three days (eq 1 and Figure S9).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

et al. 2022

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Triggering C−N bond formation with nitroaromatics and boronic acids at mild conditions is highly desirable, since most prior works were carried out under harsh conditions and sometimes suffered from poor chemo-or regioselectivity. Herein, a low-valent-tungsten-catalyzed reaction that enables the ambient temperature amination of boronic acids with nitroaromatics is disclosed. With readily available W(CO) 6 as a precatalyst under external-photosensitizer-free conditions, nitroaromatics smoothly undergo C−N coupling reactions with their boronic acid partners, delivering structurally diverse secondary amines in good yields (>50 examples, yields up to 96%). This methodology is both scalable and highly chemoselective and engages both aliphatic and aromatic boronic acid partners. The catalysis is initiated by the deoxygenation of nitroaromatics by a trans-[W(CO) 4 (PPh 3 ) 2 ] (trans-W, PPh 3 = triphenylphosphine) complex, which forms in situ via ligand replacement.

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Section: Resultsmentioning

confidence: 97%

Section: ■ Results and Discussionmentioning

confidence: 99%

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

et al. 2022

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Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO₂(nacnac)₂

2023

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Cis‐MoO2(nacnac)2 (nacnac=β‐diketiminate) can be a viable chiral‐at‐metal catalyst when its two β‐diketiminate (nacnac) ligands are N‐substituted to prevent Λ⇌Δ racemization. Even simple methyl groups raise the barriers for racemization significantly for the Bailar, Rây‐Dutt, Conte‐Hippler, and Dhimba‐Muller‐Lammertsma (DML) twists to a respectable 28.5, 37.8, 30.5, and 25.1 kcal/mol, respectively, at ωB97X‐D/6‐311+G(2d,p) (LANL2DZ for Mo) including acetonitrile solvation. The lowest energy DML barrier increases to ΔGo=27.4 kcal/mol with N‐substituted t‐butyl groups. The nacnac ligands’ electronic and steric components to the racemization barriers are discussed.

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Crystal structures and supramolecular architectures of ONO donor hydrazone and solvent exchangeable dioxidomolybdenum(VI) complexes derived from 3,5-diiodosalicyaldehyde-4-methoxybenzoylhydrazone: Hirshfeld surface analysis and interaction energy calculations

Kuriakose

Kurup

2019

Polyhedron

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Synthesis and characterization of two dioxidomolybdenum(VI) complexes bearing amidinato and pyrazolato ligands and their use in thin film growth and oxygen atom transfer reactions

Cited by 3 publications

References 49 publications

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO₂(nacnac)₂

Crystal structures and supramolecular architectures of ONO donor hydrazone and solvent exchangeable dioxidomolybdenum(VI) complexes derived from 3,5-diiodosalicyaldehyde-4-methoxybenzoylhydrazone: Hirshfeld surface analysis and interaction energy calculations

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Synthesis and characterization of two dioxidomolybdenum(VI) complexes bearing amidinato and pyrazolato ligands and their use in thin film growth and oxygen atom transfer reactions

Cited by 3 publications

References 49 publications

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics

Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO2(nacnac)2

Crystal structures and supramolecular architectures of ONO donor hydrazone and solvent exchangeable dioxidomolybdenum(VI) complexes derived from 3,5-diiodosalicyaldehyde-4-methoxybenzoylhydrazone: Hirshfeld surface analysis and interaction energy calculations

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Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO₂(nacnac)₂