Comparative Study of NS<sub>2</sub>(<i>S</i>-aryl) Pyridine-Based Dithia-Containing Ligands with Different Substituent Groups. Reactivity toward Cu(II) and Ru(II)

Teixidor, Francesç; Anglès, Pilar; Viñas, Clara; Kivekäs, Raikko; Sillanpää, Reijo

doi:10.1021/ic000903t

Cited by 10 publications

(8 citation statements)

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“…However, to this point, few SNS carbonyl complexes have been reported. Previous studies of SNS Ru families use PPh 3 or DMSO as the neutral ancillary ligand, , and empirical catalytic studies tend to compare PNP carbonyl complex 1 with SNS precatalyst 6 , which bears a PPh 3 instead of CO ligand. Herein, we describe the preparation and properties of several new SNS Ru carbonyl complexes.…”

Section: Introductionmentioning

confidence: 99%

Comparative Coordination Chemistry of PNP and SNS Pincer Ruthenium Complexes

et al. 2021

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Ruthenium carbonyl complexes supported by PNP pincer ligands are prominent catalysts for a range of hydrogenation and dehydrogenation reactions. Recently, Ru complexes with cheaper, more air stable SNS pincer ligands have emerged as attractive alternatives for the development of improved catalysts. However, there is currently a paucity of information on how the replacement of the phosphine donors in PNP ligands with the sulfur donors in SNS ligands influences the synthesis, structure, and electronic properties of the resulting metal complexes. Herein, the coordination chemistry of a series of Ru carbonyl complexes with SNS pincer ligands has been systematically compared with related PNP-ligated species. Three different SNS pincer ligands were explored including a pyridyl based NC 5 H 3 {CH 2 (S t Bu)} 2 ligand and two aliphatic ligands, HN{CH 2 CH 2 (S t Bu)} 2 and NCH 3 {CH 2 CH 2 (S t Bu)} 2 , along with different combinations of monodentate ancillary ligands. The geometric structures of the SNS and PNP Ru complexes were studied using NMR spectroscopy and X-ray crystallography. Additionally, the redox properties and electronic structures of these complexes were probed through a combination of cyclic voltammetry and DFT calculations. Overall, differences between SNS and PNP complexes extend well beyond simply modulating inductive donation to the metal and include changes in synthetic outcomes, as well as variations in geometry that impact redox behavior. Our study reveals fundamental information about the coordination chemistry of the SNS ligand, which may aid in interpreting catalytic results.

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Section: Introductionmentioning

confidence: 99%

Comparative Coordination Chemistry of PNP and SNS Pincer Ruthenium Complexes

et al. 2021

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“…No X-ray structures of free (pro)ligands presenting the OSNSO skeleton are available for comparison. However, the structural parameters of 1•H2 may be compared with those of related compounds incorporating the characteristic aryl 2-picolyl thioether scaffold [48][49][50][51]. In particular, both CH2-S (aver.…”

Section: Scheme 2 Synthesis Of the Osnso Pro-ligand 1•h2mentioning

confidence: 99%

“…In particular, both CH2-S (aver. S1 for the list of bond lengths and angles for 1•H2) [48][49][50][51].…”

Section: Scheme 2 Synthesis Of the Osnso Pro-ligand 1•h2mentioning

confidence: 99%

Cobalt complexes of an OSNSO-tetrapodal pentadentate ligand: Synthesis, structures and reactivity

Thevenin

Daran

Poli

et al. 2021

Inorganica Chimica Acta

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The novel pentadentate tetrapodal proligand 2,6-bis [(2-hydroxyphenyl)sulfanylmethyl]pyridine (1•H2) and its cobalt(II) complex [Co(1)] (2) were synthesized and characterized by several analytical (EA, ESI-MS) and spectroscopic methods (NMR or EPR, FT-IR), including X-ray crystallography for 1•H2. Cyclic voltammetry studies showed that 2 undergoes a reversible metal-based oxidation (Co II /Co III ). Complex 2 was designed to be applied to organometallic mediated radical polymerization (OMRP), however it exhibited an extremely poor solubility in non-coordinating solvents and several vinyl monomers (styrene, vinyl acetate and tert-butyl acrylate), which hampers its potential as moderator. Complex 2 has a high affinity towards Lewis bases, such as pyridine, leading to the clean formation of the monopyridine adduct 2•py, as confirmed by X-ray crystallography. In 2•py, ligand 1 is pentacoordinated to the Co II center, with the two thioether-phenolate (S,O) moieties oriented anti to each other, and the only free coordination site of the octahedron is completed by the additional pyridine, trans to the central pyridine linker of 1. The equilibrium between 2 and 2•py could be studied by 1 H NMR. Complex 2 could be cleanly and quantitatively oxidized to its diamagnetic iodo cobalt(III) analog [Co(1)I] (3), by simple reaction with iodine. The latter could then be subjected to a halide abstraction reaction, mediated by K[B(C6F5)], affording the cationic complex [Co(1)][B(C6F5)], 4. Highlights• Cobalt(II) complexes of a bis(thioether)-bis(phenolato)-pyridyl-based OSNSO-ligand.• Neutral (OSNSO)-cobalt(III) iodide and cationic (OSNSO)-cobalt(III) complexes.• XRD, NMR, CV and EPR studies.• Evaluation in radical polymerization.

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“…For related structures, see: Sellmann et al (1999); Teixidor et al (1999Teixidor et al ( , 2001; Smit et al (2004); Gilbert et al (2000). For the synthesis of the title compound, see: Reger et al (2005).…”

Section: Related Literaturementioning

confidence: 99%