Half sandwich complexes of chalcogenated pyridine based bi-(N, S/Se) and terdentate (N, S/Se, N) ligands with (η6-benzene)ruthenium(ii): synthesis, structure and catalysis of transfer hydrogenation of ketones and oxidation of alcohols (original) (raw)

Abstract

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This work investigates the synthesis and catalytic activities of novel half-sandwich Ru(II) complexes incorporating chalcogenated pyridine-based bidentate and terdentate ligands. The study identifies these ligands as effective for transfer hydrogenation of ketones and oxidation of alcohols, revealing insights into their structural properties through DFT calculations and crystallographic analysis.

Figures (11)

NMR spectra

NMR spectra

Fig. 1 ORTEP diagram of the cation of 1 with ellipsoids at the 30% probability level. Hydrogen atoms and the PF6 anions have s been omitted for clarity. Bond lengths (A): Ru-S(1) 2.3771(18), Ru-N(1) 2.095(5), Ru(1)-Cl(1) 2.3876(19). Bond angles (°): S(1)-Ru(1)}-N(1) 80.49(15), S(1}-Ru(1)}-C1(1) 93.39(6).

Fig. 1 ORTEP diagram of the cation of 1 with ellipsoids at the 30% probability level. Hydrogen atoms and the PF6 anions have s been omitted for clarity. Bond lengths (A): Ru-S(1) 2.3771(18), Ru-N(1) 2.095(5), Ru(1)-Cl(1) 2.3876(19). Bond angles (°): S(1)-Ru(1)}-N(1) 80.49(15), S(1}-Ru(1)}-C1(1) 93.39(6).

Fig. 4 ORTEP diagram of the cation of 4 with ellipsoids at the 30% probability level. Hydrogen atoms and the PF6 anions have s been omitted for clarity. Bond lengths (A): Ru-S(1) 2.3133(15), Ru-N(1) 2.098(4), Ru(1)—N(2) 2.111(5). Bond angles (°): N(1)— Ru(1)-S(1) 83.02(13), N(2)—Ru(1)-S(1) 83.13(14)

Fig. 4 ORTEP diagram of the cation of 4 with ellipsoids at the 30% probability level. Hydrogen atoms and the PF6 anions have s been omitted for clarity. Bond lengths (A): Ru-S(1) 2.3133(15), Ru-N(1) 2.098(4), Ru(1)—N(2) 2.111(5). Bond angles (°): N(1)— Ru(1)-S(1) 83.02(13), N(2)—Ru(1)-S(1) 83.13(14)

Fig. 8 Frontier Molecular Orbitals of 1-5

Fig. 8 Frontier Molecular Orbitals of 1-5

charge on Ru also facilitates the formation of ruthenium hydride needed in case of transfer hydrogenation. Thus Se containing species are expected to be more efficient for the transfer hydrogenation catalysis as well. The charges on the other atoms ; are given in Fig. 9 and Table S3 (ESI). io Experimental Physical measurement

charge on Ru also facilitates the formation of ruthenium hydride needed in case of transfer hydrogenation. Thus Se containing species are expected to be more efficient for the transfer hydrogenation catalysis as well. The charges on the other atoms ; are given in Fig. 9 and Table S3 (ESI). io Experimental Physical measurement

Om Prakash, Kamal Nayan Sharma, Hemant Joshi, Pancham Lal Gupta, Ajai K. Singh* Efficiency for transfer hydrogenation and oxidation catalyzed with structurally characterized comple:

Om Prakash, Kamal Nayan Sharma, Hemant Joshi, Pancham Lal Gupta, Ajai K. Singh* Efficiency for transfer hydrogenation and oxidation catalyzed with structurally characterized comple:

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  69. Om Prakash, Kamal Nayan Sharma, Hemant Joshi, Pancham Lal Gupta, Ajai K. Singh* Efficiency for transfer hydrogenation and oxidation catalyzed with structurally characterized complexes 1-5 is highest for Se containing bidentate ligand.