1,3-P,N hybrid ligands in mononuclear coordination chemistry and homogeneous catalysis

Rong, Mark K.; Holtrop, Flip; Slootweg, J. Chris; Lammertsma, Koop

doi:10.1016/j.ccr.2018.08.016

Cited by 33 publications

(16 citation statements)

References 154 publications

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“…Next, we explored the coordination to Ru II (Scheme 6) and the catalytic activity [4a] of the resulting complexes. Reacting 7 a,b with [Ru( p ‐cym)Cl 2 ] 2 ( p ‐cym= p ‐cymene) provided the P ‐ κ 1 complex 14 b (66 %, δ ( 31 P) 27.3 ppm).…”

Section: Resultsmentioning

confidence: 99%

Atypical and Asymmetric 1,3‐P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

Rong

Holtrop

Bobylev

et al. 2021

Chemistry A European J

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Novel seven‐membered cyclic imine‐based 1,3‐P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These “cycloiminophosphanes” possess flexible non‐isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P‐κ1‐ and P,N‐κ2‐tungsten(0) carbonyl complexes, by determining the IR frequency of the trans‐CO ligands. Complexes with [RhCp*Cl2]2 demonstrated the hemilability of the ligands, giving a dynamic equilibrium of κ1 and κ2 species; treatment with AgOTf gives full conversion to the κ2 complex. The potential for catalysis was shown in the RuII‐catalyzed, solvent‐free hydration of benzonitrile and the RuII‐ and IrI‐catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l‐menthone, as well as their P,N‐κ2‐RhIII and a P‐κ1‐RuII complexes.

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Section: Resultsmentioning

confidence: 99%

Atypical and Asymmetric 1,3‐P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

Rong

Holtrop

Bobylev

et al. 2021

Chemistry A European J

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“…The final R 1 was 0.0396 [I > 2σ(I)] and wR 2 was 0.1134 (all data). The structure for 5 was refined as a two component twin against and hklf5 file, the twin scale fraction of the second component refined to 0.419 (2). Anisotropic parameters, bond lengths and (torsion) angles for these structures are available from the cif files which can be found in the supplementary crystallographic data for this paper.…”

Section: Eurjicmentioning

confidence: 99%

“…[1] Many known mixed donor systems are based on phosphine and nitrogen functional groups. [2][3][4] Our research group has been interested in the ligand diphenyl-2-(3-methyl)indolylphosphine (L) ( Figure 1) for some time. [5,6] This ligand contains a phosphorus donor in addition to a pendent N-H functional group which has the potential to interact directly at the metal centre itself or with co-ligands within the coordination sphere.…”

Section: Introductionmentioning

confidence: 99%

Palladium and Platinum Complexes Containing Diphenyl‐2‐(3‐methyl)indolylphosphine

et al. 2020

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Syntheses and characterisation of group ten complexes containing the ligand diphenyl‐2‐(3‐methyl)indolylphosphine are presented herein. The complexes [trans‐PdCl2{PPh2(C9H8N)}2] (1), [cis‐PtCl2{PPh2(C9H8N)}2] (2), [trans‐Pd(CH3)Cl{PPh2(C9H8N)}2] (3) and [trans‐Pt(CH3)Cl{PPh2(C9H8N)}2] (4) have all been structurally characterized by X‐ray crystallography. In all cases, the ligands coordinate to the metal centres via the phosphorus donor atom (κ1‐P) and the pendent NH groups on the indolyl rings of the ligand are orientated so that there is some degree of interaction with the metal–chloride bonds. The unexpected reactivity of 4 with Na[B{3,5‐C6H3(CF3)2}4] is also reported. In this case, the product resulting from this reaction was found to be [Pt{3,5‐C6H3(CF3)2}2{PPh2(C9H8N)}2].

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“…In addition, many transition metal complexes, such as rhodium, iridium, iron, and cobalt, are known to be catalysts for hydrosilylation of alkenes. [ 6–9 ] However, they still possess many drawbacks, such as low catalytic activity and reaction selectivity. Therefore, there has been an increasing demand for cheap metal catalysts with high catalytic activity and reaction selectivity.…”

Section: Introductionmentioning

confidence: 99%

Highly active cobalt complex catalysts used for alkene hydrosilylation

Liu

Bai

et al. 2021

Applied Organom Chemis

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A series of nitrogen phosphine ligands were synthesized, and the hydrosilylation reaction of alkenes catalyzed using MCl2 in the presence of these ligands was investigated. FeCl2/1(N1, N1, N2, N2‐Tetrakis[(diphenylphosphino)methyl]ethane‐1,2‐diamine) showed low catalytic activity. MnCl2/1, CrCl3/1 and NiCl2/1 showed some catalytic activity. The CoCl2/N,P‐ligand catalyst system showed high activity as well as excellent selectivity (The selectivity of the β‐adduct was ~100%.) in the hydrosilylation reaction. CoCl2/1 showed the highest catalytic activity (~ >99.9% conversion of 1‐octene). Additionally, no α‐adduct, dehydrogenative silylation product and octane were detected.

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1,3-P,N hybrid ligands in mononuclear coordination chemistry and homogeneous catalysis

Cited by 33 publications

References 154 publications

Atypical and Asymmetric 1,3‐P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

Atypical and Asymmetric 1,3‐P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

Palladium and Platinum Complexes Containing Diphenyl‐2‐(3‐methyl)indolylphosphine

Highly active cobalt complex catalysts used for alkene hydrosilylation

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