Synthesis and characterization of new Pd(II) non-symmetrical Pincer complexes derived from thioether functionalized iminophosphoranes. Evaluation of their catalytic activity in the Suzuki–Miyaura couplings

Ramírez‐Rave, Sandra; Estudiante‐Negrete, Fabiola; Toscano, Rubén A.; Hernández‐Ortega, Simón; Morales‐Morales, David; Grévy, Jean‐Michel

doi:10.1016/j.jorganchem.2013.09.038

Cited by 42 publications

(53 citation statements)

References 63 publications

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“…A comparison with the value found for the non‐carboranyl analog SnClMe 2 I3 ( δ =17.5 ppm), more shifted with respect to the organic precursor I3‐Br ( δ =0.68 ppm), indicates again that the carboranyl derivatives show weaker Sn ··· N interactions. In any case, the shifts found for all of the organotin compounds imply only weak Sn ··· N intramolecular interactions of different strength, as proper M–N bonds cause higher shifts, from 30 to 60 ppm, depending on the metal and its coordination geometry, as described in the literature for other cyclometalated iminophosphorane complexes …”

Section: Resultssupporting

confidence: 64%

Coordinating Ability of the Iminophosphorane Group in ortho‐Carborane Derivatives

2017

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Abstract:The coordinating ability of the nitrogen donor atom of C-carboranyl iminophosphoranes was studied in different ligand systems. The analysis of organotin derivatives of the unsubstituted iminophosphorane I1 (SnMe 3 I1 and SnClMe 2 I1) and the comparison with the non-carboranyl analog (SnClMe 2 I3), reveals the reduced donor capacity of the nitrogen atom due to the closo-carborane group. To promote the coordination of this weak donor atom, new phosphine-iminophosphorane ligands (IP1 and IP2), with an extra -PPh 2 group on the other cage carbon atom, were synthesized and structurally characterized. The analysis of the products formed by the reaction of these ligands with the metal precursor cis-

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Section: Resultssupporting

confidence: 64%

Coordinating Ability of the Iminophosphorane Group in ortho‐Carborane Derivatives

2017

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“…After six successive cycles, the Cu-AIA-PC-Pd catalystr emains substantially active and no significant decreasesi nt he catalytic efficiency are observed ( Figure S22). Compared with the catalysts reported in literatures (TableS5), [73][74][75][76][77][78][79][80][81][82][83] the obtained Cu-AIA-PC-Pd also exhibits excellentc atalytic activity.T he results confirm that Cu-AIA as a2 Dcarriertos upport metal catalysts is feasible.…”

Section: Catalytic Performanceand Reaction Mechanism Analysismentioning

confidence: 65%

Amino‐Induced 2D Cu‐Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

Tang

Cai

Xie

et al. 2020

Chemistry A European J

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With the assistance of hydrogen bonds of the o‐amino group, we have successfully tuned a coordination structure from a metal–organic polyhedron (MOP) to a two‐dimensional (2D) metal–organic framework (MOF). The amino group forms hydrogen bonds with the two vicinal carboxylic groups, and induces the ligand to coordinate with copper ions to form the 2D structure. The obtained 2D Cu‐based MOF (Cu‐AIA) has been applied as an efficient heterogeneous catalyst in the aerobic epoxidation of olefins by using air as oxygen source. Without the aggregation problem of active sites in MOPs, Cu‐AIA possesses much higher reactivity than MOP‐1. Furthermore, the amino group of the framework has been used as a modifiable site through post‐synthetic metalation (PSMet) to prepare a 2D MOF‐supported Pd single‐site heterogeneous catalyst, which shows excellent catalytic performance for the Suzuki reaction. It indicates that Cu‐AIA can also work as a good 2D MOF carrier for the derivation of other heterogeneous catalysts.

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“…These factors provide the potential for hemilabile coordination of the donor ligand arms with the metal center, an important consideration in the design of pincer palladacycles [15][16][17]. This can lead to different physical and chemical properties of the donor ligand arms, resulting in preferential decoordination of one of the ligand arms, providing the opportunity to fine tune the catalytic activity of unsymmetrical pincer palladacycles [18][19][20][21]. An excellent example by Wendt and co-workers reported the hemilabile nature of nitrogen and phosphorus donor atoms by reacting with a strong nucleophile (MeLi) [22].…”

Section: Figurementioning

confidence: 99%

The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study

et al. 2016

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A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH 2 )C 6 H 3 }], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C-H bond activation, and used, along with PCN and N'CN unsymmetrical pincer palladacycles previously synthesized by the authors, to determine the extent to which the trans influence is exhibited in unsymmetrical pincer palladacycles. The trans influence is quantified by analysis of structural changes in the X-ray crystal and density functional theory (DFT) optimized structures and a topological analysis of the electron density using quantum theory of atoms in molecules (QTAIM) to determine the strength of the Pd-donor atom interaction. It is found that the trans influence is controlled by the nature of the donor atom and although the substituents on the donor-ligand affect the Pd-donor atom interaction through the varied electronic and steric constraints, they do not influence the bonding of the ligand trans to it. The data indicate that the strength of the trans influence is P > S > N. Furthermore, the synthetic route to the family of SCN pincer palladacycles presented demonstrates the potential of late stage derivitization for the effective synthesis of ligands towards unsymmetrical pincer palladacycles.

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Synthesis and characterization of new Pd(II) non-symmetrical Pincer complexes derived from thioether functionalized iminophosphoranes. Evaluation of their catalytic activity in the Suzuki–Miyaura couplings

Cited by 42 publications

References 63 publications

Coordinating Ability of the Iminophosphorane Group in ortho‐Carborane Derivatives

Coordinating Ability of the Iminophosphorane Group in ortho‐Carborane Derivatives

Amino‐Induced 2D Cu‐Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study

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