Single and double deprotonation/dearomatization of the N,S-donor pyridinophane ligand in ruthenium complexes

We describe the synthesis of a triazolyl-pyridine-based aminophosphine, N-(diphenylphosphaneyl)-6-(1-phenyl)-1H- (1,2,3-triazol-4-yl)H)N hereafter], and its palladium and platinum complexes and their catalytic application. The reaction of 1 with [M(COD)Cl 2 ] (M = Pd or Pt) afforded the cationic complex [(MCl){PN(H)N}-κ 3 -P,N,N]Cl [M = Pd (2) or Pt (3)]. Alternatively, compounds 2 and 3 were also synthesized by treating [2,6-{H 2 N(C 5 H 3 N)(C 2 HN 3 C 6 H 5 )}] (A) with [M(COD)Cl 2 ] (M = Pd or Pt), followed by the addition of stoichiometric amounts of PPh 2 Cl and Et 3 N. The neutral, dearomatized complexes [(MCl){PNN}-κ 3 -P,N,N] [M = Pd (4) or Pt (5)] were prepared by the deprotonation of the NH of 2 and 3 with 1 equiv of t BuOK. Compounds 4 and 5 were also synthesized stepwise by treating [2,6-{H 2 N(C 5 H 3 N)(C 2 HN 3 C 6 H 5 )}] (A) with [M-(COD)Cl 2 ] (M = Pd or Pt) to give intermediate complexes [{MCl 2 }2,6-{NH 2 (C 5 H 3 N)(C 2 HN 3 C 6 H 5 )-κ 2 -N,N}] [M = Pd (B) or Pt (C)], which were subsequently phosphinated. The in situ-generated PNN ligand-stabilized Pd nanoparticles from compound 2 catalyzed the annulation of o-bromobenzaldehyde with alkynes to yield indenone derivatives. Mechanistic investigations suggested that the reaction was catalyzed by Pd nanoparticles (Pd@2) generated from compound 2 and proceeded through sequential oxidative addition, alkyne insertion, and reductive elimination steps to produce indanone products.

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Cationic and Neutral Pd^II and Pt^II Pincer Complexes of Phosphinamino-Triazolyl-Pyridine [PN(H)N]: Pincer Ligand-Stabilized Palladium Nanoparticles and Their Catalytic Annulation of Internal Alkynes to Indenones

Sheokand

Balakrishna

2023

Inorg. Chem.

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A strategic approach for Csp³–H functionalization of 9H-fluorene: an acceptorless dehydrogenation and borrowing hydrogen approach

Sharma

Mondal

Samanta

et al. 2023

Catal. Sci. Technol.

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Single and double deprotonation/dearomatization of the N,S-donor pyridinophane ligand in ruthenium complexes

Abstract: We report a series of ruthenium complexes with a tetradentate N,S-donor ligand, 2,11-dithia[3.3](2,6)pyridinophane (N2S2) that undergo single and double deprotonation in the presence of a base leading to the deprotonation...

Cited by 2 publications

References 62 publications

Cationic and Neutral Pd^II and Pt^II Pincer Complexes of Phosphinamino-Triazolyl-Pyridine [PN(H)N]: Pincer Ligand-Stabilized Palladium Nanoparticles and Their Catalytic Annulation of Internal Alkynes to Indenones

Cationic and Neutral Pd^II and Pt^II Pincer Complexes of Phosphinamino-Triazolyl-Pyridine [PN(H)N]: Pincer Ligand-Stabilized Palladium Nanoparticles and Their Catalytic Annulation of Internal Alkynes to Indenones

A strategic approach for Csp³–H functionalization of 9H-fluorene: an acceptorless dehydrogenation and borrowing hydrogen approach

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Single and double deprotonation/dearomatization of the N,S-donor pyridinophane ligand in ruthenium complexes

Abstract: We report a series of ruthenium complexes with a tetradentate N,S-donor ligand, 2,11-dithia[3.3](2,6)pyridinophane (N2S2) that undergo single and double deprotonation in the presence of a base leading to the deprotonation...

Cited by 2 publications

References 62 publications

Cationic and Neutral PdII and PtII Pincer Complexes of Phosphinamino-Triazolyl-Pyridine [PN(H)N]: Pincer Ligand-Stabilized Palladium Nanoparticles and Their Catalytic Annulation of Internal Alkynes to Indenones

Cationic and Neutral PdII and PtII Pincer Complexes of Phosphinamino-Triazolyl-Pyridine [PN(H)N]: Pincer Ligand-Stabilized Palladium Nanoparticles and Their Catalytic Annulation of Internal Alkynes to Indenones

A strategic approach for Csp3–H functionalization of 9H-fluorene: an acceptorless dehydrogenation and borrowing hydrogen approach

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Cationic and Neutral Pd^II and Pt^II Pincer Complexes of Phosphinamino-Triazolyl-Pyridine [PN(H)N]: Pincer Ligand-Stabilized Palladium Nanoparticles and Their Catalytic Annulation of Internal Alkynes to Indenones

Cationic and Neutral Pd^II and Pt^II Pincer Complexes of Phosphinamino-Triazolyl-Pyridine [PN(H)N]: Pincer Ligand-Stabilized Palladium Nanoparticles and Their Catalytic Annulation of Internal Alkynes to Indenones

A strategic approach for Csp³–H functionalization of 9H-fluorene: an acceptorless dehydrogenation and borrowing hydrogen approach