Ru(II) complexes containing (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole: Synthesis, solid-state structure, computational study and catalysis in N-alkylation reactions

• Published in: Inorganica Chimica Acta Vol. 512; p. 119864
• Main Authors: Murugan, Kaliyappan, Vijayapritha, Subbarayan, Viswanathamurthi, Periasamy, Saravanan, Kandasamy, Vijayan, Paranthaman, Ojwach, Stephen O.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01-11-2020; Elsevier Science Ltd
• Subjects: Alkylation; Amines; Carbon monoxide; Catalytic activity; Chemical synthesis; Coordination compounds; DFT calculations; Hydrazines; Mass spectrometry; NMR; Nuclear magnetic resonance; Prefabrication; Ru(II) complexes; Ruthenium; Ruthenium compounds; Single crystals; Solid state; Surface analysis (chemical); π–π interaction; Catalytic activity; Ru(II) complexes; DFT calculations; π–π interaction
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2020.119864

Ruthenium(II) complexes containing (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole efficiently catalyze the N-alkylation of amines with alcohols. The reaction works under mild condition with 1 mol % of catalyst and could be performed on a small scale, providing an alternative to conventional N-alkylation reaction.
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•Ru(II) complexes with (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole were designed and synthesized.•The complexes efficiently catalyzed the N-alkylation of primary amines with alcohols.•Water as a sole by product in these catalytic reactions.
Reactions of (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole (L) with ruthenium(II) prefabricated precursors [RuHCl(CO)(EPh3)3] and [RuH2(CO)(EPh3)3] (E = P or As) afforded new Ru(II) complexes [RuCl(CO)(EPh3)2(L)] and [RuH(CO)(EPh3)2(L)] (E = P or As) (1–4). All the Ru(II) complexes (1–4) were characterized by IR, NMR spectroscopies, ESI-mass spectrometry and elemental analyses. The solid-state structures of Ru(II) complexes (2 and 3) were established by single crystal X-ray analyses and revealed distorted octahedral geometries around the ruthenium(II) ion and mono anionic bidentate N^N coordination mode for hydrazine ligand. The Ru(II) complexes 2 and 3 were also analyzed using Hirshfeld surface analysis and DFT calculations. Moreover, all the complexes (1–4) were utilized in the N-alkylation reactions of amines using alcohol. Complex 3 was found to be highly active towards N-alkylation of different aromatic amines with alcohol.