Cyclometalated phosphine-based Ir(III) pincer complex as a catalyst for Oppenauer-type oxidation of alcohols

Levy, Roy; Azerraf, Clarite; Gelman, Dmitri; Rueck‐Braun, Karola; Kapoor, Pramesh N.

doi:10.1016/j.catcom.2009.10.018

Cited by 38 publications

(12 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, they proved themself as highly active catalysts for the transfer hydrogenation of ketones [12], as well as transfer [16] and acceptorless dehydrogenation of alcohols [17].…”

Section: Introductionmentioning

confidence: 99%

New PC(sp3)P pincer complexes of platinum and palladium

Musa

Shpruhman

Gelman

2012

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

“…Moreover, they proved themself as highly active catalysts for the transfer hydrogenation of ketones [12], as well as transfer [16] and acceptorless dehydrogenation of alcohols [17].…”

Section: Introductionmentioning

confidence: 99%

New PC(sp3)P pincer complexes of platinum and palladium

Musa

Shpruhman

Gelman

2012

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

“…On the outset of our studies, we demonstrated unusual activity of such complexes in the transfer hydrogenation of ketones (Scheme ). − More recently, we also showed different reactivity of two stereoisomers in oxidative addition and reductive elimination reactions and, consequently, in the transfer dehydrogenation of alkanes (Scheme ). In this work, we inquire about possible origins of different reactivities of the stereoisomeric Ir(III) complexes bearing a prototypical 1,8-bis(diisopropylphosphino)triptycene ligand and the influence of their stereochemistry on their catalytic activity in alkenes isomerization.…”

Section: Introductionmentioning

confidence: 94%

Stereoisomerism as an Origin of Different Reactivities of Ir(III) PC(sp³)P Pincer Catalysts

et al. 2020

Self Cite

View full text Add to dashboard Cite

Two stereoisomers of pentacoordinate iridium(III) hydridochloride with triptycene-based PC(sp 3 )P pincer ligand (1,8bis(diisopropylphosphino)triptycene), 1 and 2, differ by the orientation of hydride ligand relative to the bridgehead ring of triptycene. According to DFT/B3PW91/def2-TZVP calculations performed, an equatorial Cl ligand can relatively easily change its position in 1, whereas that is not the case in 2. Both complexes 1 and 2 readily bind the sixth ligand to protect the empty coordination site. Variable temperature spectroscopic (NMR, IR, and UV−visible) studies show the existence of two isomers of hexacoordinate complexes 1•MeCN, 2•MeCN, and 2•Py with acetonitrile or pyridine coordinated trans to hydride or trans to metalated C(sp 3 ), whereas only the equatorial isomer is found for 1• Py. These complexes are stabilized by various intramolecular noncovalent C−H•••Cl interactions that are affected by the rotation of isopropyls or pyridine. The substitution of MeCN by pyridine is slow yielding axial Py complexes as kinetic products and the equatorial Py complexes as thermodynamic products with faster reactions of 1•L. Ultimately, that explains the higher activity of 1 in the catalytic alkenes' isomerization observed for allylbenzene, 1-octene, and pent-4-enenitrile, which proceeds as an insertion/elimination sequence rather than through the allylic mechanism.

show abstract

“…Surprisingly, no Oppenauer-type oxidations were reported with iridacycles, although there is one report on the use of an iridium-pincer complex (outside the scope of the review) [ 69 ].…”

Section: Iridacycles As Transfer Hydrogenation Catalystsmentioning

confidence: 99%

Ruthenacycles and Iridacycles as Transfer Hydrogenation Catalysts

Ritleng

Vries

2021

Molecules

View full text Add to dashboard Cite

In this review, we describe the synthesis and use in hydrogen transfer reactions of ruthenacycles and iridacycles. The review limits itself to metallacycles where a ligand is bound in bidentate fashion to either ruthenium or iridium via a carbon–metal sigma bond, as well as a dative bond from a heteroatom or an N-heterocyclic carbene. Pincer complexes fall outside the scope. Described are applications in (asymmetric) transfer hydrogenation of aldehydes, ketones, and imines, as well as reductive aminations. Oxidation reactions, i.e., classical Oppenauer oxidation, which is the reverse of transfer hydrogenation, as well as dehydrogenations and oxidations with oxygen, are described. Racemizations of alcohols and secondary amines are also catalyzed by ruthenacycles and iridacycles.

show abstract

Cyclometalated phosphine-based Ir(III) pincer complex as a catalyst for Oppenauer-type oxidation of alcohols

Cited by 38 publications

References 32 publications

New PC(sp3)P pincer complexes of platinum and palladium

New PC(sp3)P pincer complexes of platinum and palladium

Stereoisomerism as an Origin of Different Reactivities of Ir(III) PC(sp³)P Pincer Catalysts

Ruthenacycles and Iridacycles as Transfer Hydrogenation Catalysts

Contact Info

Product

Resources

About

Cyclometalated phosphine-based Ir(III) pincer complex as a catalyst for Oppenauer-type oxidation of alcohols

Cited by 38 publications

References 32 publications

New PC(sp3)P pincer complexes of platinum and palladium

New PC(sp3)P pincer complexes of platinum and palladium

Stereoisomerism as an Origin of Different Reactivities of Ir(III) PC(sp3)P Pincer Catalysts

Ruthenacycles and Iridacycles as Transfer Hydrogenation Catalysts

Contact Info

Product

Resources

About

Stereoisomerism as an Origin of Different Reactivities of Ir(III) PC(sp³)P Pincer Catalysts