Mixed Donor Ligands

Tannert, René; Pfaltz, Andreas

doi:10.1002/9781118299715.ch6

Cited by 6 publications

(2 citation statements)

References 274 publications

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“…Electronic and steric characteristics of phosphines can be readily modified by their functionalization at various positions. Among them, aminophosphines stand out, which contain fundamentally different N and P donor groups. − A wide range of substituents at the heteroatoms, as well as the ability to act as polydentate ligands for different transition metals, allow one to design aminophosphines for many practical applications: biomolecular chemistry, as antitumor agents, activators of small molecules, , and homogeneous , and enantioselective catalysts . Complexes with α-aminophosphines are effective catalysts in reactions of hydroformylation of styrene, , Heck reactions between olefine and aryl halides, , and Suzuki-Miyaura and decarboxylative C–C couplings .…”

Section: Introductionmentioning

confidence: 99%

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Afonin,

Martynenko,

Kolybalov

et al. 2023

Inorg. Chem.

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There is unceasing interest toward transformations of phosphine derivatives, which are facilitated by transition metals. We report a facile Pd(II)-and Pt(II)-assisted P−C bond cleavage in a luminescent 2-phenylbenzothiazole-based αmethylaminophosphine (PCN, 1). Specifically, reactions between 1 and [M(COD)Cl 2 ] (M = Pd, Pt; COD = cycloocta-1,5-diene) in different solvents (methylene chloride, acetonitrile, pyridine, toluene) resulted in the formation of PPh 2 − , captured either as a bridging ligand in binuclear complexes with a {M 2 (PPh 2 ) 2 } moiety or as an adduct to COD in [Pt 2 (PPh 2 COD) 2 Cl 2 ]. The heterocyclic part transforms to annulated c-CN + species with a 1,2-dihydroquinazoline cycle formed. In the presence of pyridine as a base, annulated form c-CN + destabilizes and undergoes reverse cyclization transforming to deprotonated CN form. Quantum-chemical density functional theory (DFT) calculations predict that a crucial step in the reactions involves proton transfer from the N atom of the amino group of PCN to a neighboring molecule. A combination of high photophysical sensitivity of c-CN + toward its immediate environment and rich structural capabilities in assembling (c-CN) 2 2+ pairs in different crystal packings in a family of phases with the general formula (c-CN) 2 [M 2 (PPh 2 ) 2 Cl 4 ] allows one to fine-tune the luminescence properties of the latter. The results were rationalized as a variation of π−π intercationic spacings, which tunes the degree of excitedstate charge transfer between c-CN + cations. As a result, compounds with relatively short interplanar π−π-separation between the cations show a stronger charge-transfer-mediated bathochromic shift.

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Section: Introductionmentioning

confidence: 99%

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Afonin,

Martynenko,

Kolybalov

et al. 2023

Inorg. Chem.

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“…Mixed-donor chelating ligands, 8 which possess both a soft and a hard donor atom, have been successfully applied in transition metal catalysis due to their hemilabile properties. 9 In palladium catalysis, ancillary hard donors (O-/N-donors) can stabilize the metal centers through weak coordination with the soft palladium centers.…”

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confidence: 99%

An indole-amide-based phosphine ligand enabling a general palladium-catalyzed sterically hindered Suzuki–Miyaura cross-coupling reaction

Chen

Yuen

et al. 2022

Org. Biomol. Chem.

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Catalytic Approach to Diverse α‐Aminoboronic Acid Derivatives by Iridium‐Catalyzed Hydrogenation of Trifluoroborate‐Iminiums

Šterman

Košmrlj

Žigart³

et al. 2021

Adv Synth Catal

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A series of structurally diverse benzyl protected trifluoroborate‐ammoniums were prepared in good to high yields by an efficient hydrogenation of corresponding trifluoroborate‐iminiums using Crabtree's catalyst. Subsequent N‐ and B‐deprotections were demonstrated on selected examples to provide several α‐aminoboronic acids. Preliminary experiments on asymmetric version of the reaction indicated a correlation between E/Z‐ratio in the trifluoroborate‐iminium substrate and enantioselectivity. The broad scope, operational simplicity and efficiency of the presented method imply its high potential for a facile access to libraries of α‐aminoboronic acid derivatives that can be used in medicinal chemistry applications and beyond.

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Mixed Donor Ligands

Cited by 6 publications

References 274 publications

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

An indole-amide-based phosphine ligand enabling a general palladium-catalyzed sterically hindered Suzuki–Miyaura cross-coupling reaction

Catalytic Approach to Diverse α‐Aminoboronic Acid Derivatives by Iridium‐Catalyzed Hydrogenation of Trifluoroborate‐Iminiums

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