Bi- and tetrametallic complexes of the noble metals with PNP-ligands

Sarcher, Christian; Lebedkin, Sergei; Kappes, Manfred M.; Fuhr, Olaf; Roesky, Peter W.

doi:10.1016/j.jorganchem.2013.05.016

Cited by 7 publications

(2 citation statements)

References 68 publications

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“…Recently, Kappes, Fuhr, Roesky, and co-workers described the synthesis of the N -functionalized DPPA-type ligand 43 (Scheme ), the diazenyl analog of the amino derivative 8 (see Scheme ). Ligand 43 exhibits a single 31 P NMR resonance at 69.0 ppm (in CDCl 3 ), which is consistent with the value found for 8 (69.3 ppm in CDCl 3 , Table ). Reaction of 43 with 2 equiv of [AuCl(THT)] afforded the corresponding dinuclear complex 44 (Scheme ), characterized by a 31 P NMR singlet resonance at 88.3 ppm (CDCl 3 ).…”

Section: Nitrogen-based Functionalizationsmentioning

confidence: 98%

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

2016

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The aim of this review is to highlight how the diversity generated by N-substitution in the well-known short-bite ligand bis(diphenylphosphino)amine (DPPA) allows a fine-tuning of the ligand properties and offers a considerable scope for tailoring the properties and applications of their corresponding metal complexes. The various N-substituents include nitrogen-, oxygen-, phosphorus-, sulfur-, halogen-, and silicon-based functionalities and directly N-bound metals. Multiple DPPA-type ligands linked through an organic spacer and N-functionalized DRPA-type ligands, in which the PPh2 substituents are replaced by PR2 (R = alkyl, benzyl) groups, are also discussed. Owing to the considerable diversity of N-functionalized DPPA-type ligands available, the applications of their mono- and polynuclear metal complexes are very diverse and range from homogeneous catalysis with well-defined or in situ generated (pre)catalysts to heterogeneous catalysis and materials science. In particular, sustained interest for DPPA-type ligands has been motivated, at least in part, by their ability to promote selective ethylene tri- or tetramerization in combination with chromium. Ligands and metal complexes where the N-substituent is a pure hydrocarbon group (as opposed to N-functionalization) are outside the scope of this review. However, when possible, a comparison between the catalytic performances of N-functionalized systems with those of their N-substituted analogs will be provided.

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Section: Nitrogen-based Functionalizationsmentioning

confidence: 98%

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

2016

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“…The use of preparative pathways gives access to several structural alterations via the production of a straightforward P-N bond [12,13]. P-N-P skeletons are more versatile than P-C-P skeletons, and tiny modifications in substituents result in dramatic alterations in the P-N-P angle and structure around the whole P-centers [14][15][16]. As a result, by modifying the substituents, their coordination characteristics and structural features may be drastically altered.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel Bis(phosphino)amine-Ruii(acac)2 Complexes, and Investigation of Catalytic Activity in Transfer Hydrogenation

Karakaş

Işık

Aydemir

et al. 2022

Middle East Journal of Science

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In this study, reactions of (PPh2)2NCH2CH2N(PPh2)2 (L1) and {(PPh2)2NCH2CH2}3N (L2) with [RuII(acac)2(CH3CN)2] led to the production of new dinuclear complex [Ru(acac)2]2(L1) (1) and trinuclear complex [Ru(acac)2]3(L2) (2). Complex 1 and 2 are excellent candidates for the role of catalyst precursors in the transfer hydrogenation (TH) of acetophenone and its derivatives. Compared to complex (1), the trinuclear complex (2) is an exceptional catalyst, producing the corresponding alcohols in 98–99% yields in 20 minutes at 80 oC (TOF≤300 h-1) for the TH process. A comparison of the catalytic properties of the complexes is also briefly discussed. Complex structures have also been characterized by combining nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR), and elemental analysis.

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Immobilization of [Pd{(Ph₂P)₂N(CH₂)₃Si(OCH₃)₃‐κP,P'}X₂] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki‐Miyaura Catalysts

et al. 2017

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Two palladium complexes, [Pd{(Ph2P)2N(CH2)3Si(OCH3)3‐κP,P'}X2], X=Cl (2), Br (3), were synthesized and characterized by spectroscopic methods and X‐ray crystallography. Complexes 2 and 3 contain a PdP2X2 square planar coordination sphere exhibiting small endocyclic P–Pd–P angles [71.49(4) and 71.53(5)°, respectively], the magnitude of which is controlled by the formation of the Pd–P–N–P four‐membered chelating ring. Complexes 2 and 3 were found to be efficient catalysts in the Suzuki‐Miyaura cross‐coupling reaction of aryl bromides with phenylboronic acid at ambient or elevated temperature. At 100 °C, using 0.1 mol% of palladium loading, high conversions were observed even after 15 min. Both complexes were immobilized onto STx‐1 montmorillonite clay via their −Si(OMe)3 moiety, a process investigated by X‐ray powder diffraction, X‐ray fluorescence spectrometry, solid‐state 31P NMR spectroscopy and Scanning Electron Microscopy. The immobilized complexes, as heterogenized catalysts, displayed higher activity in the Suzuki‐Miyaura coupling compared to that of the free complexes. The recyclability of the former was also explored.

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Bi- and tetrametallic complexes of the noble metals with PNP-ligands

Cited by 7 publications

References 68 publications

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

Synthesis of Novel Bis(phosphino)amine-Ruii(acac)2 Complexes, and Investigation of Catalytic Activity in Transfer Hydrogenation

Immobilization of [Pd{(Ph₂P)₂N(CH₂)₃Si(OCH₃)₃‐κP,P'}X₂] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki‐Miyaura Catalysts

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Bi- and tetrametallic complexes of the noble metals with PNP-ligands

Cited by 7 publications

References 68 publications

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

Synthesis of Novel Bis(phosphino)amine-Ruii(acac)2 Complexes, and Investigation of Catalytic Activity in Transfer Hydrogenation

Immobilization of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3‐κP,P'}X2] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki‐Miyaura Catalysts

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Immobilization of [Pd{(Ph₂P)₂N(CH₂)₃Si(OCH₃)₃‐κP,P'}X₂] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki‐Miyaura Catalysts