Phosphaalkenes

Dugal-Tessier, Julien; Conrad, Eamonn D.; Dake, Gregory R.; Gates, Derek P.

doi:10.1002/9781118299715.ch10

Cited by 19 publications

(18 citation statements)

References 83 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The introduction of a PC functionality in a pincer ligand enhances the reactivity remarkably . The chemistry of low-coordinate phosphorus compounds, such as phosphinidenes and phosphaalkenes, is an active research area, as compounds with PC double bonds possess low-lying π* orbitals, which can act as effective π acceptors in the coordination of transition metals. , The η 1 coordination mode of phosphaalkenes toward metal atoms or ions is common, but the η 2 coordination mode of phosphaalkenes is also known (Figure ). , Chelating phosphaalkene complexes have also been described .…”

Section: Introductionmentioning

confidence: 99%

Versatile Coordination Modes of Triphospha-1,4-pentadiene-2,4-diamine

et al. 2018

View full text Add to dashboard Cite

1,3,5-Triphospha-1,4-pentadiene-2,4-diamine reacts with [M(CO)L] (M = Mo, L = nbd (norbornadiene); M = W, L = 2 CHCN) to give the chelate complexes [M(CO)(PMes{C(NHCy)PMes}-κ P ,P)]. In contrast, an unusual intramolecular rearrangement occurred with [Cu(CHCN)]PF leading to the dimeric copper(I) complex [Cu(CNCy){PHMesPMesC(NHCy)PMes-κ P ,P}](PF). The mechanism of the rearrangement was supported by quantum-mechanical calculations. The transition-metal complexes were characterized by multinuclear NMR spectroscopy, mass spectrometry, infrared spectroscopy, and X-ray crystallography.

show abstract

Section: Introductionmentioning

confidence: 99%

Versatile Coordination Modes of Triphospha-1,4-pentadiene-2,4-diamine

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Phosphaalkenes with a PC double bond are an interesting class of phosphorus compounds, which possess an extremely low lying π* orbital and thus serve as strong π acceptors toward transition metals . We are currently interested in the application of this particular ligand property in organometallic chemistry. − This paper describes the synthesis of a novel pyridine-based PNP-pincer type phosphaalkene ligand that exhibits noninnocent behavior on group 9 metals.…”

Section: Introductionmentioning

confidence: 99%

Unsymmetrical PNP-Pincer Type Phosphaalkene Ligands Protected by a Fused-Ring Bulky Eind Group: Synthesis and Applications to Rh(I) and Ir(I) Complexes

et al. 2016

View full text Add to dashboard Cite

We recently reported that 2-(phospholanylmethyl)-6-(2-phosphaethenyl)pyridine (PPEP) with a 2,4,6-tri-tert-butylphenyl group (Mes*) as steric protection of the PC bond serves as a noninnocent ligand on Ir(I), leading to extremely high reactivity toward metal–ligand cooperative activation of ammonia and acetonitrile. The high reactivity is largely due to the strong π-accepting properties of the PC bond. However, PPEP had a stability problem that provokes the loss of the PC bond on other transition metals, including Rh(I), and restricts its utilization. This paper describes the synthesis of Eind-PPEP protected by an octaethyl-s-hydrindacen-4-yl group (Eind) instead of Mes*. The fused-ring bulky Eind group successfully prevents the loss of the PC bond and enables us to compare the reactivity of Rh(I) and Ir(I) complexes toward ammonia. The complex K[RhCl(Eind-PPEP*)], bearing a dearomatized Eind-PPEP* ligand, undergoes simple ligand displacement to give [Rh(NH3)(Eind-PPEP*)], whereas the iridium analogue K[IrCl(Eind-PPEP*)] causes N–H bond cleavage to form [Ir(NH2)(Eind-PPEP)]. DFT calculations indicate a thermodynamic cause of the metal-dependent product change.

show abstract

“…The use of phenylphosphorus compounds for the construction of organometallic complexes, exemplified by the “Wilkinson catalyst”, was a big leap for catalytic reactions toward molecular accuracy . It also inspired the study of electrostatic and steric effects in ligand design. , These two effects, however, are usually entangled and change with ligand changes. Typically, the distances between ligands and the metal center are sensitive to their sizes as well as their geometric angles (Scheme A,B).…”

mentioning

confidence: 99%

“…All the Au-P-MVs were capable of converting mesitylene to 2,4,6-trimethylbromobenzene within 5 h, while non-metalated MVs as control showed negligible activity (Figure B, entries 1–6). We also synthesized Au-N-MVs using a N-based linker, 4′,4′′′,4′′′′′-nitrilotris((1,1′-biphenyl)-4-carboxylic acid), , as control. X-ray photoelectron spectroscopy analysis confirmed that all Au(III) species were coordinated (SI, Figures S118 and S119), while elemental analysis revealed a higher loading of Au(III) in Au-P-MVs than that in Au-N-MVs (SI, Table S12).…”

mentioning

confidence: 99%

Molecular Vises for Precisely Positioning Ligands near Catalytic Metal Centers in Metal–Organic Frameworks

Yan

Yang

et al. 2020

J. Am. Chem. Soc.

View full text Add to dashboard Cite

We report the construction of a molecular vise by pairing a tritopic phenylphosphorus(III) linker and a monotopic linker in opposite positions within a metal−organic framework. The angle between these linkers at metal sites is fixed upon changing the functionality in the monotopic linker, while the distance between them is precisely tuned. This distance within the molecular vise is accurately measured by 1 H− 31 P solid-state nuclear magnetic resonance spectroscopy. This unveils the impact of the distance on catalytic performance without interference from electrostatic effects or changes in the angle of the ligand, which is unprecedented in classic organometallic complexes.

show abstract

Phosphaalkenes

Cited by 19 publications

References 83 publications

Versatile Coordination Modes of Triphospha-1,4-pentadiene-2,4-diamine

Versatile Coordination Modes of Triphospha-1,4-pentadiene-2,4-diamine

Unsymmetrical PNP-Pincer Type Phosphaalkene Ligands Protected by a Fused-Ring Bulky Eind Group: Synthesis and Applications to Rh(I) and Ir(I) Complexes

Molecular Vises for Precisely Positioning Ligands near Catalytic Metal Centers in Metal–Organic Frameworks

Contact Info

Product

Resources

About