Zirconium-Catalyzed Alkene Hydrophosphination and Dehydrocoupling with an Air-Stable, Fluorescent Primary Phosphine

Bange, C; Mucha, Neil T.; Cousins, Morgan E.; Gehsmann, Abigail C.; Singer, Anna; Truax, Taylor; Higham, Lee J.; Waterman, Rory

doi:10.3390/inorganics4030026

Cited by 7 publications

(4 citation statements)

References 31 publications

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“…Primary phosphines are under-reported in catalytic hydrophosphination, despite a resurgence in interest over the last several years. ,,,,,, Expansion of catalytic hydrophosphination to include primary phosphines beyond PhPH 2 would therefore be of value. Photocatalytic hydrophosphination undertaken with CyPH 2 (Cy = cyclohexyl) and MesPH 2 (Mes = 2,4,6-trimethylphenyl) using 1 gave high conversion (Table ).…”

Section: Resultsmentioning

confidence: 99%

“…Both turnover number and turnover frequency for all reactions were substantially higher under irradiation than prior reports, and these reactions maintained the high selectivity for secondary phosphine product formation when using 2 equiv of PhPH 2 as seen previously. 24,44,45 Both catalytic hydrophosphination under blacklight (TON = 20 and TOF = 13.3 h −1 ) and 253.7 nm (TON = 20 and TOF = 40 h −1 ) lamps substantially outperform thermal hydrophosphination of styrene with 1 (TON = 18 and TOF = 1.5 h −1 ). The greater reactivity at 253.7 nm may be a result of relative light intensity rather than the specific wavelength (vide inf ra).…”

Section: ■ Introductionmentioning

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%

Section: ■ Introductionmentioning

confidence: 99%

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

et al. 2018

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“…Despite the advances in leveraging electronic effects to impart oxidative stability to primary phosphines, some of these substrates are relatively large. Despite their steric profile, the substrates were reasonably effective. , While interesting, it is more relevant to this story to focus on work with alkyne substrates. Initial reactions with internal alkynes, to avoid the C–H bond activation of terminal alkynes that plagued early studies, gave the vinyl phosphines but at an unexpectedly sluggish pace.…”

Section: Hydrophosphinationmentioning

confidence: 99%

Triamidoamine-Supported Zirconium Compounds in Main Group Bond-Formation Catalysis

Waterman

2019

Acc. Chem. Res.

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Conspectus The rationale to pursue long-term study of any system must be sound. Quick discoveries and emergent fields are more than temptations. They remind us to ask what are we gaining through continued study of any system. For triamidoamine-supported zirconium, there has been a great deal gained with yet more ahead. Initial study of the system taught much that is applied to catalysis. Cyclometalation of a trimethylsilyl substituent of the ancillary ligand, abbreviated (N3N) when not metalated for simplicity, via C–H bond activation is facile and highly reversible. It has allowed for the synthesis of a range of Zr–E bonds, which are of fundamental interest. More germane, cyclometalation has emerged as our primary product liberation step in catalysis. Cyclometalation also appears to be a catalyst resting state, despite how cyclometalation is a known deactivation step for many a compound in other circumstances. Catalysis with triamidoamine-supported zirconium has been rich. Rather than summarizing the breadth of reactions, a more detailed report on the dehydrocoupling of phosphines and hydrophosphination is provided. Both reactions demonstrate the outward impact that the study of (N3N)Zr-based catalysis has afforded. Dehydrocoupling catalysis, or bond formation via loss of hydrogen, is particular to 3p and heavier main group elements. The reaction has been important in the formation of E–E and E–E′ bonds in the main group for molecular species and materials. While study of this reaction at (N3N)Zr compounds provides key insights into mechanism, discoveries in the area of P–P and Si–Si bond formation with (N3N)Zr derivatives as catalysts have greater reach than merely the synthesis of main group element containing products. For example, that work has informed design principles for the identification of catalysts that transfer low-valent fragments. The successful application of these principles was evident in the discovery of a catalyst that transfers phosphinidene (“PR”) to unsaturated substrates. Hydrophosphination exhibits perfect atom economy in the formation of P–C bonds. The reaction can proceed without a catalyst, but the purpose of a catalyst is enhanced reactivity and selectivity. Nevertheless, significant challenges in this reaction remain. In particular, (N3N)Zr compounds have demonstrated high activity in hydrophosphination and readily utilize unactivated unsaturated organic molecules, challenging substrates for any heterofunctionalization reaction. This activity has led to not only impressive metrics in the catalysis but access to previously untouched substrates and formation of unique products. The particular properties of the (N3N)Zr system that engage in this reactivity may influence other heterofunctionalization reactions. The recently discovered photocatalytic hydrophosphination with (N3N)ZrPRR′ compounds already appears to be general rather than unique and may drive additional bond formation catalysis among early transition-metal compounds.

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“…Marks et al − reported that organolanthanoid compounds such as C catalyze intramolecular hydrophosphinations to produce cyclic phosphines such as that shown in eq . More recently intermolecular hydrophosphinations have been reported that are catalyzed by complexes of Ca, − Ba, Zr, − Sn, and Fe − (see Chart for examples). …”

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confidence: 99%

Self-Replication of Chelating Diphosphines via Pt(0)-Catalyzed Hydrophosphination

et al. 2019

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The air-stable, functionalized diphosphine Ph2PCH2CH2P(CH2CH2CO2Me)2 (L1) is the ligand for the Pt(0) complex that efficiently catalyzes the production of L1 from Ph2PCH2CH2PH2 and methyl acrylate. The mechanism proposed for this catalysis is consistent with the following observations: (1) the only product detected upon treatment of [Pt(nbe)3] (nbe = η2-norbornene) with L1, even in the ratio Pt:L1 of 10:1, is the bis(chelate) complex [Pt(κ2-L1)2]; (2) complex 1 reacts with Ph2PCH2CH2PH2 to release L1; (3) complex 1 does not react with CH2CHCO2Me even when an excess of acrylate is present in high concentration; (4) the Pt(0)-catalyzed deuterophosphination of CH2CHCO2Me by Ph2PCH2CH2PD2 produced exclusively the isotopologue Ph2PCH2CH2P(CH2CHDCO2Et)2 (L1-d 2) as a mixture of diastereoisomers; (5) in a competition experiment, CH2CHCO2Me reacted significantly more rapidly with Ph2PCH2CH2PH2 than with Ph2PCH2CH2PD2. The scope of this Pt(0)-catalyzed process has been extended to Ph2PCH2CH2P(CH2CH2Z)2 (Z = CO2Et, CO2 t Bu, CN, CONH2, CONMe2), and it has the potential to be a general, atom-efficient route to many other functionalized diphosphines.

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Zirconium-Catalyzed Alkene Hydrophosphination and Dehydrocoupling with an Air-Stable, Fluorescent Primary Phosphine

Cited by 7 publications

References 31 publications

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

Triamidoamine-Supported Zirconium Compounds in Main Group Bond-Formation Catalysis

Self-Replication of Chelating Diphosphines via Pt(0)-Catalyzed Hydrophosphination

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