Synthesis of New Bidentate Phosphine Ligands Containing Saturated Phosphorus Heterocycles

Field, L. D.; Thomas, I.

doi:10.1021/ic951374+

Cited by 13 publications

(8 citation statements)

References 46 publications

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“…In previous reports, intramolecular hydrophosphination of 3 gave exclusively the phospholane product(s). ,,, Selective formation of a six- over a five-membered ring is the result of 1,2-insertion versus 2,1-insertion during catalysis with 1 . However, it is known that derivatives of 3 can spontaneously ring-close upon irradiation. ,, To test if this were a noncatalytic pathway compound 3 was synthesized independently. Treatment of 3 with 5 mol % of 1 under irradiation provided high conversions (85%) to 4 at ambient temperature (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

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Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

et al. 2018

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Catalytic hydrophosphination using [κ 5 -N,N,N,N,C-(Me 3 SiNCH 2 CH 2 ) 2 NCH 2 CH 2 NSiMe 2 CH 2 ]Zr (1) under photolysis substantially enhances activity and avails greater substrate scope. Quantitative conversions of alkenes to secondary phosphines are reached in as little as 20 min at ambient temperature with 1 under ultraviolet or visible irradiation. A larger class of unactivated alkenes are now facile substrates under photolysis conditions, and 1 can engage in a previously unknown tandem inter/intramolecular hydrophosphination of 1,4-pentadiene to give the heterocyclic phosphorinane product. Computational and spectroscopic data indicate that photoexcitation of 1 at a variety of wavelengths results in P n → Zr d charge transfer. This excitation appears to accelerate catalysis by promoting substrate insertion at the Zr−P bond based on experimental observations.

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Section: Resultsmentioning

confidence: 99%

“…However, it is known that derivatives of 3 can spontaneously ring-close upon irradiation. 34,59,60 To test if this were a noncatalytic pathway compound 3 was synthesized independently. Treatment of 3 with 5 mol % of 1 under irradiation provided high conversions (85%) to 4 at ambient temperature (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

et al. 2018

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“…CoCl 2 , [Rh(COD) 2 ](CF 3 SO 3 ), dmpe, depe, and dmpm were purchased from Strem Chemical and used without further purification. Syntheses of BPE5, dmpbz, Co(dmpe) 2 H, , Co(dedpe) 2 H, Co(depe) 2 H, [Rh(dmpe) 2 ](CF 3 SO 3 )/Rh(dmpe) 2 H, , [Rh(depe) 2 ](CF 3 SO 3 ), [Rh(dcpe) 2 ](CF 3 SO 3 ), [Rh(dppe) 2 ](CF 3 SO 3 ), [Co(CH 3 CN) 6 ](BF 4 ) 2 , and Rh(dppe) 2 H were previously reported elsewhere.…”

Section: Methodsmentioning

confidence: 99%

Understanding the Relationship Between Kinetics and Thermodynamics in CO₂Hydrogenation Catalysis

et al. 2017

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Catalysts that are able to reduce carbon dioxide under mild conditions are highly sought after for storage of renewable energy in the form of a chemical fuel. This study describes a systematic kinetic and thermodynamic study of a series of cobalt and rhodium bis(diphosphine) complexes that are capable of hydrogenating carbon dioxide to formate under ambient temperature and pressure. Catalytic CO2 hydrogenation was studied under 1.8 and 20 atm of pressure (1:1 CO2/H2) at room temperature in tetrahydrofuran with turnover frequencies (TOF) ranging from 20 to 74 000 h–1. The catalysis was followed by 1H and 31P NMR spectroscopy in real time under all conditions to yield information about the rate-determining step. The cobalt catalysts displayed a rate-determining step of hydride transfer to CO2, while the hydrogen addition and/or deprotonation steps were rate limiting for the rhodium catalysts. Thermodynamic analysis of the complexes provided information on the driving force for each step of catalysis in terms of the catalyst hydricity (ΔG°H– ), acidity (pK a), and free energy for H2 addition (ΔG°H2 ). Linear free-energy relationships were identified that link the kinetic activity for catalytic hydrogenation of CO2 to formate with the thermodynamic driving force for the rate-limiting steps of catalysis. The catalyst exhibiting the highest activity, Co(dmpe)2H, was found to have hydride transfer and hydrogen addition steps that were each downhill by approximately 6 to 7 kcal mol–1, and the deprotonation step was thermoneutral. This indicates the fastest catalysts are the ones that most efficiently balance the free energy relationships of every step in the catalytic cycle.

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“…With diprimary diphosphine 126 and , -dienes, the reactions were performed under irradiation at room temperature in the presence of a slight excess of diene, leading to saturated heterocycles (phosphorinanes) [48]. The addition of a radical initiator did not affect the outcome of the photochemical process.…”

Section: Hydrophosphination Under Radical Conditionsmentioning

confidence: 99%

Hydrophosphination of Unactivated Alkenes, Dienes and Alkynes: A Versatile and Valuable Approach for the Synthesis of Phosphines

Delacroix

Gaumont

2005

COC

142

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The last years have seen many advances in the field of organometallic catalysis. Motivating much of the work has been the potential for discovering new catalytic reactions, which can be used for the synthesis of bulky chemicals and fine chemical intermediates. Since the efficiency and the selectivity of the catalyst mainly rely on the structure of the ligand, there is a great interest in the design and the synthesis of new ligands (amines, aminoalcohols, thioether, phosphines etc). From all of them, phosphine derivatives are the most widely used with transition metal catalysts. Different approaches have allowed to prepare phosphine derivatives: nucleophilic substitution of a P-chloro derivative, nucleophilic substitution using metal phosphide, C-P cross coupling etc. A greener way to phosphines is the addition of a P-H bond to a multiple bond since no atom loss is observed (atom economy concept). These reactions are mainly carried out in the presence of radical initiators or under basic conditions. Acidic and neutral media were also proposed. A few recent examples reported the use of a metal activation. This review is designed to remember some of the early aspects of hydrophosphination reactions using phosphines, protected or not, and unactivated or slightly activated alkenes, dienes and alkynes and to focus on the more promising results obtained in this field for the last 15 years. The reactions involving pentavalent phosphorus derivatives (phosphine-oxide, thiophosphines, phosphonate and phosphate derivatives etc.) are not concerned b y this chapter.

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Synthesis of New Bidentate Phosphine Ligands Containing Saturated Phosphorus Heterocycles

Cited by 13 publications

References 46 publications

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

Understanding the Relationship Between Kinetics and Thermodynamics in CO₂Hydrogenation Catalysis

Hydrophosphination of Unactivated Alkenes, Dienes and Alkynes: A Versatile and Valuable Approach for the Synthesis of Phosphines

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Synthesis of New Bidentate Phosphine Ligands Containing Saturated Phosphorus Heterocycles

Cited by 13 publications

References 46 publications

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

Understanding the Relationship Between Kinetics and Thermodynamics in CO2Hydrogenation Catalysis

Hydrophosphination of Unactivated Alkenes, Dienes and Alkynes: A Versatile and Valuable Approach for the Synthesis of Phosphines

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Product

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Understanding the Relationship Between Kinetics and Thermodynamics in CO₂Hydrogenation Catalysis