Synthesis and Characterization of Ruthenium(II) Hydrido and Hydroxo Complexes Bearing the 2,6-Bis(di-<i>tert</i>-butylphosphinomethyl)pyridine Ligand

Gibson, Dorothy H.; Pariya, Chandi; Mashuta, Mark S.

doi:10.1021/om030659o

Cited by 31 publications

(20 citation statements)

References 13 publications

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“…In order to provide comparisons to PNP Ru dicarbonyl complexes, which are key catalyst deactivation species, dicarbonyl versions of the aliphatic and pyridyl SNS complexes were next targeted for synthesis . The t Bu SN py S Ru dicarbonyl complex [Ru( t Bu SN py S)(CO) 2 Cl][PF 6 ] ( 5–2CO ), was synthesized cleanly via ligand addition to the coordination polymer [Ru(CO) 2 (Cl) 2 ] n (Scheme ), a method which has been used to obtain similar species containing pyridyl PNP or terpyridine ligands. The identity of 5–2CO was verified by single crystal X-ray diffraction (vide infra) as well as the observation of two relatively high frequency carbonyl stretches at 2082 and 2031 cm –1 in the IR spectrum (Table ).…”

Section: Resultsmentioning

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: Resultsmentioning

confidence: 99%

Comparative Coordination Chemistry of PNP and SNS Pincer Ruthenium Complexes

et al. 2021

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“…[61] This result can be related to the recent reactivity observed by Milstein and co-workers for analogous Ru complexes. [55] Gibson et al independently reported the formation of some Ru complexes with 12 tBu in 2004 (Scheme 13), [62] simultaneously with the first application of this catalyst system for the acceptorless dehydrogenation of alcohols by Milstein and co-workers. [51] In the former report, a RuÀOH species that arose from facile deprotonation of an elusive intermediate aquo complex was also discussed, as well as some other interesting compounds.…”

Section: Other Chemistry With Rutheniummentioning

confidence: 96%

Neutral Tridentate PNP Ligands and Their Hybrid Analogues: Versatile Non‐Innocent Scaffolds for Homogeneous Catalysis

Vlugt¹,

Reek²

2009

Angew Chem Int Ed

420

145

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Ligands in coordination chemistry and homogeneous catalysis are traditionally "static" spectators that do not actively participate in the catalytic cycle. However, such classic systems do not provide additional "handles" that could facilitate or trigger alternative productive reaction pathways. Recent advances in the use of novel nitrogen-centered pincer systems have unveiled interesting opportunities for cooperative catalysis. The chemistry of pyridine-derived, neutral ligands is discussed, with a specific focus on their non-innocent behavior and potential as facilitators for metal-mediated organic transformations. This overview should provide inspiration and an incentive to incorporate non-innocent ligands and their metal complexes within old and new homogeneously catalyzed reactions.

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“…These spectroscopic features are in line with an analogous PNP-Ru pincer complex reported by Mashuta and co-workers. 61 Treatment of cis-[ t Bu 4 L-RuCl-(CO) 2 ]Cl with a mild oxidative decarbonylating agent, Me 3 NO, facilitates loss of a CO ligand, and subsequent deprotection gives H 4 L-RuCl 2 (CO). 62 The 1 H and 31 P NMR spectra of the product indicates a ∼1:3 mixture of cis and trans isomers.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis and Reactivity of Zr MOFs Assembled from P^NN^NP-Ru Pincer Complexes

et al. 2019

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Three isostructural Zr metal–organic frameworks have been synthesized from PNNNP-Ru pincer metallolinkers bearing different combinations of ancillary ligands (1, Zr6O4(OH)4(OAc)4{cis-(PNNNP)RuCl2(CO)}2; 2, Zr6O4(OH)4(O2CH)4{(PNNNP)RuCl(CO)2}2Cl2; 3, Zr6O4(OH)4(OAc)4{cis-/trans-(PNNNP)RuCl2(CO)}2; PNNNP = 2,6-(HNPAr2)2C5H3N; Ar = p-C6H4CO2 –). The structure and composition of the PNNNP-Ru pincer MOFs have been determined using synchrotron X-ray powder diffraction, solid- and solution-state NMR spectroscopy, IR spectroscopy, and elemental analysis. Reaction of 2 with KOtBu results in deprotonation of an NH group of the PNNNP-RuCl(CO)2 linkers. Subsequent treatment with Me3NO removes a Ru-coordinated CO ligand, generating 2-b, which proved to be a recyclable catalyst for the hydrosilylation of aryl aldehydes with Et3SiH. A similar postsynthetic treatment of 1 and 3 does not generate active catalysts, highlighting the importance of precatalyst design and activation. A homogeneous analogue of 2-b also showed inferior catalytic performance, demonstrating the benefit of catalyst immobilization.

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Synthesis and Characterization of Ruthenium(II) Hydrido and Hydroxo Complexes Bearing the 2,6-Bis(di-tert-butylphosphinomethyl)pyridine Ligand

Cited by 31 publications

References 13 publications

Comparative Coordination Chemistry of PNP and SNS Pincer Ruthenium Complexes

Comparative Coordination Chemistry of PNP and SNS Pincer Ruthenium Complexes

Neutral Tridentate PNP Ligands and Their Hybrid Analogues: Versatile Non‐Innocent Scaffolds for Homogeneous Catalysis

Synthesis and Reactivity of Zr MOFs Assembled from P^NN^NP-Ru Pincer Complexes

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Synthesis and Characterization of Ruthenium(II) Hydrido and Hydroxo Complexes Bearing the 2,6-Bis(di-tert-butylphosphinomethyl)pyridine Ligand

Cited by 31 publications

References 13 publications

Comparative Coordination Chemistry of PNP and SNS Pincer Ruthenium Complexes

Comparative Coordination Chemistry of PNP and SNS Pincer Ruthenium Complexes

Neutral Tridentate PNP Ligands and Their Hybrid Analogues: Versatile Non‐Innocent Scaffolds for Homogeneous Catalysis

Synthesis and Reactivity of Zr MOFs Assembled from PNNNP-Ru Pincer Complexes

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Synthesis and Reactivity of Zr MOFs Assembled from P^NN^NP-Ru Pincer Complexes