Arylpalladium compounds containing an alcohol functionality: hindered rotation around the Pd-C bond and reactivity toward styrene and carbon monoxide. Comments on carbon-oxygen bond shortening in late-transition-metal alkoxides

1993 ◽  
Vol 12 (5) ◽  
pp. 1639-1647 ◽  
Author(s):  
Paul L. Alsters ◽  
Jaap Boersma ◽  
Wilberth J. J. Smeets ◽  
Anthony L. Spek ◽  
Gerard Van Koten
Keyword(s):  
Carbon Monoxide ◽  
Transition Metal ◽  
Late Transition Metal ◽  
Metal Alkoxides ◽  
Hindered Rotation ◽  
Late Transition ◽  
Oxygen Bond

scholarly journals Magnesium-Stabilised Transition Metal Formyl Complexes: Structures, Bonding, and Ethenediolate Formation

2021 ◽  
Author(s):  
Joe Parr ◽  
Andrew J. P. White ◽  
Mark Crimmin
Keyword(s):  
Carbon Monoxide ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Late Transition Metal ◽  
Late Transition ◽  
Bonding Mode

Herein we report the first comprehensive series of crystallographically characterised transition metal formyl complexes. In these complexes, the formyl ligand is trapped as part of a chelating structure between a transition metal (Cr, Mn, Fe, Co, Rh, W, and Ir) and a magnesium (Mg) cation. Calculations suggest that this bonding mode results in significant oxycarbene-character of the formyl ligand. Electron-rich late-transition metal complexes have the highest oxycarbene-character to the bonding and are the most stable in solution. Further reaction of a heterometallic Cr---Mg formyl complex results in a rare example of C–C coupling and formation of an ethenediolate complex. These results show that well-defined transition metal formyl complexes are potential intermediates in the homologation of carbon monoxide.

Molecular oxofluorides OMFn of nickel, palladium and platinum: oxyl radicals with moderate ligand field inversion

2021 ◽  
Author(s):  
Lin Li ◽  
Helmut Beckers ◽  
Tony Stüker ◽  
Tilen Lindič ◽  
Tobias Schlöder ◽  
...  
Keyword(s):  
Transition Metal ◽  
Ligand Field ◽  
Late Transition Metal ◽  
Late Transition ◽  
Oxo Compounds ◽  
High Valent ◽  
Oxygen Bond ◽  
Field Inversion ◽  
Oxo Ligands

High-valent late transition metal oxo compounds attracted attention because of their peculiar metal–oxygen bond. Their oxo ligands exhibit an electrophilic and distinct radical oxyl (O˙−) rather than the more common nucleophilic (O2−) character.

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