Carbon‐Carbon Bond Activation at Chromium(I): An 11‐Electron Complex Cleaving Dialkynes DOI Creative Commons
Lutz H. Gade, Felix Braun,

Tim Bruckhoff

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 28, 2024

An 11-electron T-shaped chromium(I) complex was obtained by reduction of a PNP-supported chromium(II) iodide complex. Its d

Language: Английский

Diverging Reactivity in Anilidophosphine Supported Group III Complexes DOI Creative Commons

Florian Hett,

Benjamin Wittwer,

Stephanie Bereiter

et al.

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

Abstract We report the synthesis of scandium and yttrium halide complexes with bidentate, monoanionic anilidophosphine (PN) ligands general formula 2 MX (M = Sc ( 1‐X ), Y 2‐X ); X Cl 1‐Cl / 2‐Cl I 1‐I 2‐I ). Attempts to functionalize these by salt metathesis reaction revealed that chlorido are quite unreactive precursors, whereas iodo readily engage in a broad variety reactions. azide 1‐N 3 2‐N ) as well heavy cyanate M(OC Pn Sc; P 1‐OCP As (1‐ OCAs M Y; 2‐OCP 2‐OCAs )). Furthermore, amido phosphanido M( HMesityl) N 1‐NHMes , 2‐NHMes 1‐PHMes 2‐PHMes reported. synthesize benzyl type M(Benzyl) Sc, Y, La drastic differences reactivity group III metal ions. While displayed elimination KPN without formation defined complexes, for lanthanum, C‐H activation chemistry has been observed, yielding ‐ate complex 3‐CH .

Language: Английский

Citations

0
C═C Dissociative Imination of Styrenes by a Photogenerated Metallonitrene DOI Creative Commons
Till Schmidt‐Räntsch, Hendrik Verplancke, Annemarie Kehl

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(9), P. 3421 - 3426

Published: Sept. 3, 2024

Photolysis of a platinum(II) azide complex in the presence styrenes enables C=C double bond cleavage upon dissociative olefin imination to aldimido (Pt

Language: Английский

Citations

2
T‐shaped 14 Electron Rhodium Complexes: Potential Active Species in C‐H Activation DOI Creative Commons

Leon K. Paschai Darian,

Joachim Ballmann, Lutz H. Gade

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 15, 2024

Abstract Two T‐shaped 14‐electron rhodium complexes 2 a and b , “framed” thus stabilized by PNP pincer ligands have been synthesized. The bis( t ‐butyl)phosphine derived Bu ‐rhodium complex was isolated from pentane as the more stable cyclometalated Rh(III) hydrido found to be in equilibrium with 14e − Rh(I) aT which itself could directly crystallized upon change of solvent. cyclometallation is suppressed using an adamantyl substituted Ad ligand give analogous species through agostic interaction one C−Hs. Depending on solvent, reacted ethylene either π‐coordination ( 4 ) or C−H activation giving hydrido‐vinyl both isomers being solution. Complex reversibly activate arenes form hydrido‐aryl complexes.

Language: Английский

Citations

1
Mononuclear Palladium(I) Aryl Complexes Performs Cross-Coupling Reactions with Organic Halides DOI Creative Commons
Tianqi Xia, Linhong Long, Xuebing Leng

et al.

Published: April 22, 2024

Mononuclear Pd(I) species represent the least understood Pd intermediates in Pd-catalyzed reactions and isolable complexes of type are exceedingly rare. Herein, we report synthesis characterization mononuclear bear-ing aryl ligands, namely [(IPr)Pd(ArTrip-R-p)] (ArTrip-R-p = 4-R-2,6-bis(2’,4’,6’-triisopropylphenyl)phenyl, R H, CF3), as well their with organic halides. The were prepared from [(IPr)PdCl2]2 corresponding lithium salts have been characterized by various spectroscopic methods. EPR spectroscopy calculation studies suggest nature. Reactivity using [(IPr)Pd(ArTrip-CF3-p)] representative revealed capability complex activating carbon-halogen bonds iodide benzyl In para-substituted bromides, C(aryl)-C(benzyl) cross-coupling products formed moderate to good yields. Kinetic studies, radical trapping experiments, theoretical calculations point out that likely sequential steps stepwise oxidative addition reaction bromide involving Pd(II) intermediate followed reductive elimination resulting Pd(III) intermediates.

Language: Английский

Citations

1
Modular Synthesis of Monoanionic PN Ligands Leads to Unexpected Structural Diversity in Lanthanum Chemistry DOI Creative Commons

Benjamin Wittwer,

Florian Hett,

Michael Seidl

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(43), P. 20448 - 20461

Published: Oct. 15, 2024

We report a new synthetic entry to series of

Language: Английский

Citations

1
T‐shaped 14 Electron Rhodium Complexes: Potential Active Species in C‐H Activation DOI Creative Commons

Leon K. Paschai Darian,

Joachim Ballmann, Lutz H. Gade

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 15, 2024

Abstract Zwei T‐förmige 14‐Elektronen‐Rhodiumkomplexe, 2 a und b , wurden durch PNP‐Pincer Liganden „eingerahmt“ somit stabilisiert. Der Bis( t ‐butyl)phosphin‐PNP‐Komplex wurde als stabilerer cyclometallierter Rh(III)‐hydrido‐Komplex aus Pentan isoliert, welcher sich im thermodynamischen Gleichgewicht mit dem T‐förmigen 14e − Rh(I)‐Komplex 2aT befindet, der selbst, bei Änderung des Lösungsmittels, direkt kristallisiert werden konnte. Die Cyclometallierung wird Verwendung Adamantyl‐substituierten PNP Ad ‐Liganden unterdrückt, die analoge Rh(I)‐Spezies erhalten, eine agostische Wechselwirkung einem Adamantyl‐C−Hs stabilisiert wird. Abhängig vom Lösungsmittel reagierte Komplex Ethylen entweder π‐Koordination ( 4 ) oder C−H‐Aktivierung, unter Bildung einer Hydrido‐Vinyl‐Rh(III)‐Spezies wobei beide Isomere in Lösung befinden. reagiert reversibler C−H Aktivierung Aromaten, Hydrido‐Aryl‐Rh(III)‐Komplexe gebildet werden.

Citations

0
Investigating Arylazoformamide Ligands in Palladium(II) Precatalysts through the Suzuki–Miyaura Cross-Coupling Reaction DOI
Laxmi Tiwari, Elliott B. Hulley, Kristopher V. Waynant

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Herein, is the reported synthesis and utilization of redox-active arylazoformamide (AAF) ligands in palladium(II) precatalysts for Suzuki-Miyaura cross-coupling reaction. Complexes were formed from 2 equiv an AAF ligand with Pd(II)Cl

Language: Английский

Citations

0
Carbon‐Carbon Bond Activation at Chromium(I): An 11‐Electron Complex Cleaving Dialkynes DOI Creative Commons
Lutz H. Gade, Felix Braun,

Tim Bruckhoff

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 28, 2024

An 11-electron T-shaped chromium(I) complex was obtained by reduction of a PNP-supported chromium(II) iodide complex. Its d

Language: Английский

Citations

0