Highly electron rich alkyl- and dialkyl-N-pyrrolidinyl phosphines: an evaluation of their electronic and structural properties

Clarke, Matthew L.; Holliday, Gemma L.; Slawin, Alexandra M. Z.; Woollins, J. Derek

doi:10.1039/b108467d

Cited by 67 publications

(54 citation statements)

References 29 publications

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“…[18] The ν CO value at 1974 cm -1 for IIIγ is close to that found for [RhCl(CO)(PPh 3 ) 2 ] (1965 cm -1 ), [24] thus suggesting similar electronic properties for the γ-P,N-1 ligand and triphenylphosphane. Table 1 shows quite typical geometrical features and metric parameters for a complex of type RhCl(CO)L 2 (i.e.…”

Section: Coordinationmentioning

confidence: 61%

“…: L = trialkyl-, dialkyl-N-pyrrolidinyl-, or α-amino-phosphanes), namely a nearly ideal square-planar geometry around the rhodium atom with mutually trans phosphorus atoms. [18,24] [25][26][27][28] All the above results show that the α-and γ-P,N ligands adopt the same coordination mode in rhodium chloride complexes and undergo an identical ligand redistribution process (see Scheme 3).…”

Section: Coordinationmentioning

confidence: 74%

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Amino‐phosphanes in Rh^I‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

et al. 2005

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The catalytic properties of rhodium complexes containing the α‐, β‐, or γ‐amino‐phosphane ligands Ph2PCH2NEt2 (α‐P,N‐1), Ph2PCH(Ar)NHPh [α‐P,N‐2; Ar = η6(o‐C6H4Cl)Cr(CO)3], Ph2PCH2NPh2 (α‐P,N‐3), Ph2PCH2CH(Ph)NHPh (β‐P,N), Ph2PCH2(o‐C6H4–NMe2) (γ‐P,N‐1), Ph2PCH(o‐C6H4–CH2NHPh) (γ‐P,N‐2), and the α,β‐diamino‐phosphane ligand Et2NCH2P(Ph)CH2CH(Ph)NHPh (α,β‐N,P,N), in styrene hydroformylation have been examined. The results show that the activity increases when the number of backbone carbon atoms linking P and N decreases from 3 to 1. IR and 31P HPNMR studies in solution show that all P,N ligands adopt exclusively a κ1‐P coordination mode in rhodium chloride carbonyl complexes under high CO pressure. In the solid state a κ1‐P‐α‐amino‐phosphane coordination has been ascertained by X‐ray methods in trans‐[RhCl(CO)(γ‐P,N‐1)2]. In contrast, an equilibrium between the κ2‐P,N and κ1‐P‐coordination modes has been observed as a function of the CO pressure for the complex containing the β‐P,N ligand. The basicity of the dangling amino group also plays an important role on the catalytic activity and a mechanism involving the nitrogen function in the catalytic cycle is proposed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Coordinationmentioning

confidence: 61%

Section: Coordinationmentioning

confidence: 74%

Amino‐phosphanes in Rh^I‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

et al. 2005

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“…The TOFs for the 2-furylbased [23] and the 1-pyrrolyl-based [24] ligand were only slightly different from that of the default phenyl residue by factors of 12 and 0.8, respectively. In contrast, the pyrrolidinyl group [25] led to an increase of three orders of magnitude, affording a TOF of 8.6 h…”

mentioning

confidence: 86%

Carboxylation of Arene CH Bonds with CO₂: A DFT‐Based Approach to Catalyst Design

Uhe¹,

Hölscher²,

Leitner³

2011

Chemistry A European J

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A prototypical catalytic cycle for the direct carboxylation of unactivated arene C-H bonds with CO(2) based on ruthenium(II) pincer complexes as catalysts is proposed and investigated by density functional theory (DFT) methods. The energetic span model is used to predict the turnover frequency (TOF) of various potential catalysts, evaluating their efficiency for this reaction. In addition to modifications of the catalyst structure, we also investigated the effect of the substrate, the solvent, and the influence of a base on the thermodynamics and kinetics of the reaction. Turnover frequencies in the range of 10(5)-10(7) h(-1) are predicted for the best systems. Alternative reaction pathways that might prevent the reaction are also investigated. In all cases, either the respective intermediates are found to be unstable or activation barriers are found to be very high, thereby indicating that these alternative pathways will not interfere with the proposed catalytic cycle. As a result, several ruthenium pincer complexes are suggested as very promising candidates for experimental investigation as catalysts for the carboxylation of arene C-H bonds with CO(2).

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“…We have recently demonstrated that phosphines derived from two N-bound pyrrolidine groups and one alkyl or aryl group are amongst the strongest r-donor ligands, and surprisingly are even more electron rich than tris(N-pyrrolidinyl)phosphine [5]. We have also examined the ability of P-N containing phosphines to function as catalysts [6] and recently studied structural facets including cone angle effects [7]. We have now extended our studies to investigate the properties of the new phosphine formed from 5,10-dihydrophenazine -in part to establish if it possible to distort the phenazine backbone sufficiently to obtain bidentate coordination -and since (1).…”

mentioning

confidence: 99%

The preparation and complexation of 5,10-bis(diphenylphosphino)phenazine

Zubiri¹,

Milton²,

Cole‐Hamilton³

et al. 2004

Inorganic Chemistry Communications

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Highly electron rich alkyl- and dialkyl-N-pyrrolidinyl phosphines: an evaluation of their electronic and structural properties

Cited by 67 publications

References 29 publications

Amino‐phosphanes in Rh^I‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

Amino‐phosphanes in Rh^I‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

Carboxylation of Arene CH Bonds with CO₂: A DFT‐Based Approach to Catalyst Design

The preparation and complexation of 5,10-bis(diphenylphosphino)phenazine

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Highly electron rich alkyl- and dialkyl-N-pyrrolidinyl phosphines: an evaluation of their electronic and structural properties

Cited by 67 publications

References 29 publications

Amino‐phosphanes in RhI‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

Amino‐phosphanes in RhI‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

Carboxylation of Arene CH Bonds with CO2: A DFT‐Based Approach to Catalyst Design

The preparation and complexation of 5,10-bis(diphenylphosphino)phenazine

Contact Info

Product

Resources

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Amino‐phosphanes in Rh^I‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

Amino‐phosphanes in Rh^I‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

Carboxylation of Arene CH Bonds with CO₂: A DFT‐Based Approach to Catalyst Design