Carbonyl and olefin hydrosilylation mediated by an air-stable phosphorus(<scp>iii</scp>) dication under mild conditions

Andrews, Ryan J.; Chitnis, Saurabh S.; Stephan, Douglas W.

doi:10.1039/c9cc02460c

Cited by 42 publications

(29 citation statements)

References 50 publications

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“…With respect to the p‐block, DIP complexes are known for Groups 13, 14,, 15 and 16, centres. Such complexes have found use, for example, in Lewis acid mediated catalysis including C–F bond allylation, although in such scenarios, hemi‐lability (chemical non‐innocence) of the supporting ligands rather than redox non‐innocence can be prized …”

Section: Introductionmentioning

confidence: 99%

Diiminepyridine‐Supported Phosphorus(I) and Phosphorus(III) Complexes: Synthesis, Characterization, and Electrochemistry

et al. 2020

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Diiminepyridines (DIP) are popular redox “non‐innocent” ligands with widespread application in late, first‐row transition metal mediated catalysis and coordination chemistry. Here, we report the isolation and characterization of a pair of phosphorus coordination complexes in the +1 and +3 oxidation states supported by the same ligand framework bearing sterically imposing and electron‐releasing tBu substituents on the imine carbons of the DIP backbone. Electrochemical analysis demonstrates that the DIP scaffold can retain its ability to serve as an electron reservoir when coordinated to a reduced pnictogen centre, with a reversible reduction observed for the PI complex.

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Section: Introductionmentioning

confidence: 99%

Diiminepyridine‐Supported Phosphorus(I) and Phosphorus(III) Complexes: Synthesis, Characterization, and Electrochemistry

et al. 2020

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“…BCF‐mediated hydrosilylation of carbonyls was first reported by Piers and co‐workers in 1996, however there are few examples which result in the complete reduction of the carbonyl to a methylene group . Given the benchtop activity observed for nitrenium ion 2 to affect this reaction, we were interested in expanding this work.…”

Section: Figurementioning

confidence: 96%

Nitrenium Salts in Lewis Acid Catalysis

Mehta

Goicoechea

2020

Angewandte Chemie

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Molecular compounds featuring nitrogen atoms are typically regarded as Lewis bases and are extensively employed as donor ligands in coordination chemistry or as nucleophiles in organic chemistry. By contrast, electrophilic nitrogen‐containing compounds are much rarer. Nitrenium cations are a new family of nitrogen‐based Lewis acids, the reactivity of which remains largely unexplored. In this work, nitrenium ions are explored as catalysts in five organic transformations. These reactions are the first examples of Lewis acid catalysis employing nitrogen as the site of substrate activation. Moreover, these compounds are readily accessed from commercially available reagents and exhibit remarkable stability toward moisture, allowing for benchtop transformations without the need to pretreat solvents.

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“…No reaction was observed between pyridine N-oxide or 4-dimethylamino pyridine ande ither 1 or 2 (Scheme 3a,b). In contrast, 2:1a dducts 3(pyo) 2 and 4(pyo) 2 were readily isolated from reaction involving 3 and 4,e videncing the increasing Lewis acidity of the predominantly planar compounds relative to their bent analogues (Scheme 3c). Both compounds have been isolated and structurally characterized by crystallography ( Figure 9).…”

Section: Implications For Reactivitymentioning

confidence: 99%

“…Stephan exploited as trained hemilabile ligand at phosphorus(III) cationsf or imparting air stabilityt oC ÀFb ondreduction catalysts (A). [2] Arduengo used tethered trianionic substituents to enforce planarb icyclic geometries at phosphorus, arsenic, and antimony compounds (B), resulting in ambiphilic reactivity. [3] Radosevichh as done pioneeringw ork in evolvingn ew geometry constrained main-group compounds includings ystems featuring constrained P III triamidest hat exhibit catalytic activity (C).…”

Section: Introductionmentioning

confidence: 99%

Periodicity in Structure, Bonding, and Reactivity for P-Block Complexes of a Geometry-Constraining Triamide Ligand

Marczenko

Zurakowski

Kindervater

et al. 2019

Preprint

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The use of pincer ligands to access non-VSEPR geometries at main-groupc enters is an emerging strategy for elicitingn ew stoichiometric and catalytic reactivity.A sp art of this effort, severald ifferent tridentatet rianionic substituents have to dateb een employed at ar ange of different centrale lements, providing ap atchworkd ataset that precludes rigorouss tructure-function correlation.A na nalysis of periodic trendsi ns tructure (solid, solution, and computation), bonding, and reactivity based on systematic variation of the central element( P, As, Sb, or Bi)w ith retentiono fa single tridentate triamides ubstituent is reported herein. In this homologous series, the centrale lement can adopt either ab ent or planar geometry.T he tendency to adopt planarg eometries increases descending the group with the phosphorus triamide( 1)a nd its arsenic congener (2)e xhibiting bent conformations,a nd the antimony (3)a nd bismuth (4)a naloguese xhibiting ap redominantly planar structure in solution.T his trend has been rationalized using an energy decomposition analysis. Ar arep hase-dependent dynamic covalentd imerizationw as observed for 3 and the associated thermodynamic parameters were establishedq uantitatively. Planarg eometries were found to engender lower LUMO energiesa nd smaller band gaps than bent ones, resulting in different reactivity patterns.T hese results provide ab enchmark dataset to guidef urtherr esearchi nt his rapidlye merging area.

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Carbonyl and olefin hydrosilylation mediated by an air-stable phosphorus(iii) dication under mild conditions

Abstract: The air-stable Lewis acid [(terpy)PPh][B(C6F5)4]21 mediates the hydrosilylation of aldehydes, ketones, and olefins. The mechanism of these hydrosilylations is considered.

Cited by 42 publications

References 50 publications

Diiminepyridine‐Supported Phosphorus(I) and Phosphorus(III) Complexes: Synthesis, Characterization, and Electrochemistry

Diiminepyridine‐Supported Phosphorus(I) and Phosphorus(III) Complexes: Synthesis, Characterization, and Electrochemistry

Nitrenium Salts in Lewis Acid Catalysis

Periodicity in Structure, Bonding, and Reactivity for P-Block Complexes of a Geometry-Constraining Triamide Ligand

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