Synthesis and Catalytic Properties of a Carbometalated Half-Sandwich Ru(II) Complex Bearing a Rigid Polyaromatic Tether

Abstract

We describe the synthesis and catalytic studies of a prototypical coordinatively rigid carbometalated half-sandwich Ru­(II) complex bearing a rigid polyaromatic tether. This compound represents a rare example of the nonplanar pincer complex with an unusual coordination environment. Despite being coordinatively and electronically saturated, the carbometalated complex showed the ability to activate and transfer hydrogen to polar and nonpolar double bonds. The catalytic activity of the complex was benchmarked in the Ru-catalyzed chemoselective hydrogenation of α,β-unsaturated ketones. Our initial mechanistic studies indicate that the hydrogenation is operated via an inner-sphere mechanism that proceeds via dihydride intermediates.

Aktivierung von Diorganyl‐bis(pyridylimino)isoindolid‐Aluminiumkomplexen mit sichtbarem Licht und deren organometallische Radikalreaktivität

“…Die Autoren zitierten weitere Referenzen innerhalb der Hintergrundinformationen [56–108] . Ablagenummern: (https://www.ccdc.cam.ac.uk/services/structures?id=doi:10.1002/anie.202402885) 2313487 (für 2‐Amino‐5‐mesityl‐3‐methylpyridin), 2313446 (für 1‐AlPh 2 ), 2313488 (für 2‐AlMe 2 ), 2313489 (für 2‐AlEt 2 ), 2313490 (für 2‐Al i Bu 2 ), 2313491 (für 2‐Al t Bu 2 ), 2313492 (für 2‐AlPh 2 ), 2313493 (für 2‐AlCl 2 ), 2313485 (für 2‐Al(CH=CH 2 ) 2 ), 2313494 (für 2‐Al(C≡C‐TMS) 2 ), 2313495 (für 3‐AlMe 2 ), 2313496 (für 3‐AlPh 2 ) enthält zusätzliche kristallographische Daten für diesen Artikel.…”

Visible‐Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity

“…The authors have cited additional references within the Supporting Information [56–108] . Deposition Number(s) (https://www.ccdc.cam.ac.uk/services/structures?id=doi:10.1002/anie.202402885) 2313487 (for 2‐amino‐5‐mesityl‐3‐methylpyridine), 2313446 (for 1‐AlPh 2 ), 2313488 (for 2‐AlMe 2 ), 2313489 (for 2‐AlEt 2 ), 2313490 (for 2‐Al i Bu 2 ), 2313491 (for 2‐Al t Bu 2 ), 2313492 (for 2‐AlPh 2 ), 2313493 (for 2‐AlCl 2 ), 2313485 (for 2‐Al(CH=CH 2 ) 2 ), 2313494 (for 2‐Al(C≡C‐TMS) 2 ), 2313495 (for 3‐AlMe 2 ), 2313496 (for 3‐AlPh 2 ) contain(s) the supplementary crystallographic data for this paper.…”

Theoretical DFT Investigation of Structure and Electronic Properties of η5-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes

“…The study of organometallic compounds is a central area of research in inorganic and organic chemistry for many years, with a particular focus on half-sandwich species [1][2][3][4]. They are characterized by a metal ion coordinated by two organic ligands and have proven to be of great interest in recent decades due to their potential applications in the fields of catalysis, materials science, and electronics [5][6][7][8]. Among the different types, those containing η 5 -cyclopentadienyl (Cp) ligands have garnered significant attention, as Cp is known to form stable complexes with transition metals and is a common feature in many industrially relevant catalysts and materials [9][10][11][12].…”