P,N-type phosphaalkene-based Ir(<scp>i</scp>) complexes: synthesis, coordination chemistry, and catalytic applications

Gupta, Priyanka; Drexler, Hans‐Joachim; Wingad, Richard L.; Wass, Duncan F.; Baráth, Eszter; Beweries, Torsten; Hering‐Junghans, Christian

doi:10.1039/d3qi00142c

Cited by 3 publications

(2 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…selectivity, TOF) are targeted, this performance is similar to the best existing examples. 29–33,39,43…”

Section: Resultsmentioning

confidence: 99%

“…24 The reaction pathway includes dehydrogenation of simple alcohol, base-catalyzed aldol condensation reaction and rehydrogenation of the aldol product. 25 Our group 26–33 and others 34–49 have been seeking new homogeneous catalysts for ethanol upgrading via Guerbet chemistry. Despite these recent advances, there is still significant scope for further catalyst development.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Backbone-functionalised ruthenium diphosphine complexes for catalytic upgrading of ethanol and methanol to iso-butanol

Sama,

Doyle,

Kariuki

et al. 2024

Dalton Trans.

Self Cite

View full text Add to dashboard Cite

show abstract

“…selectivity, TOF) are targeted, this performance is similar to the best existing examples. 29–33,39,43…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Backbone-functionalised ruthenium diphosphine complexes for catalytic upgrading of ethanol and methanol to iso-butanol

Sama,

Doyle,

Kariuki

et al. 2024

Dalton Trans.

Self Cite

View full text Add to dashboard Cite

show abstract

Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

Walsgrove,

Percival,

Gates

2023

Chemistry A European J

View full text Add to dashboard Cite

Understanding free radical addition to multiple bonds is important to elucidating the mechanistic details of addition polymerization reactions, albeit the fleeting radical intermediates are very difficult to detect by conventional methodologies. Muon spin spectroscopy (μSR) is a highly sensitive method that can detect radical species at 106 spins (cf. EPR: 1012 spins, NMR: 1018 spins). Herein, we employ μSR to detect the radical‐addition products from three 1‐phosphabutadiene monomers, P‐analogues of isoprene. We show that muonium (Mu), a “light” H‐atom surrogate, adds predominantly at the C4 position of the P1=C2−C3=C4 moiety to give unprecedented 1‐phosphaallyl radicals as the major products. Our structural assignments are supported by assignment of muon, phosphorus and proton hyperfine coupling constants using DFT‐calculations. A minor radical product is also detected that is tentatively assigned to an PC3‐heterocyclic free radical. On the basis of DFT‐predictions, we speculate that its formation may involve initial addition of Mu+ at the C3 position followed by electron capture. These studies provide rare insights into the prospective radical (or cationic) polymerization of 1‐phosphabutadienes, which have previously been polymerized using anionic initiation.

show abstract

Synthesis, Structure, and Catalytic Activity of Cyclometalated Iridium Complexes with a Bidentate POC Ligand

Polukeev

2023

Eur J Inorg Chem

View full text Add to dashboard Cite

Synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand is presented. Metalation of POC‐H (di‐tert‐butyl(phenoxy)phosphane) with [Ir(COD)Cl]2 proceeded rapidly at room temperature and afforded mixture of (POC)(POC‐H)IrHCl (1a) and (POC)(COD)IrHCl (1b), from which complexes (POC)(L)IrHCl where L = PPh3 (1c), bipyridine (1d) and [2,2'‐bipyridine]‐6,6'‐diol (1e) were prepared through ligand exchange. The compounds were tested in acceptorless dehydrogenation of 1‐phenylethanol and transfer dehydrogenation of ethanol in a context of comparison with pincer counterparts (POCOP)IrHCl and (PCN)IrHCl. An attempt to prepare a dihydride complex from 1e led to dimeric complex [(POC)(bipy‐diol‐)IrH]2 (3) that could explain the low activity of 1e. DFT studies provided insight into POC‐H vs POCOP‐H metalation mechanism.

show abstract

P,N-type phosphaalkene-based Ir(i) complexes: synthesis, coordination chemistry, and catalytic applications

Abstract: Phosphaalkenes are an emerging class of ligands with unique electronic properties that can be regarded as tuneable variants of the ubiquitous CO ligand. Our group has recently reported the synthesis...

Cited by 3 publications

References 75 publications

Backbone-functionalised ruthenium diphosphine complexes for catalytic upgrading of ethanol and methanol to iso-butanol

Backbone-functionalised ruthenium diphosphine complexes for catalytic upgrading of ethanol and methanol to iso-butanol

Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

Synthesis, Structure, and Catalytic Activity of Cyclometalated Iridium Complexes with a Bidentate POC Ligand

Contact Info

Product

Resources

About