C,Cʹ-Ru to C,Bʹ-Ru Isomerisation in Bis(phosphine)Ru Complexes of [1,1ʹ-Bis(ortho-carborane)]

Chemical Communications ◽

10.1039/d1cc06119d ◽

2021 ◽

Author(s):

Rebekah Jeans ◽

Georgina Rosair ◽

Alan Jeffrey Welch

Keyword(s):

Ru Complexes ◽

Carborane Ligand

We report herein the first example of the controlled isomerisation of a C,Cʹ-bound (to metal) bis(ortho-carborane) ligand to C,Bʹ-bound with no other change in the molecule. Since the C and...

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Ruthenium(II) Complexes Bearing Thioether-Appended α- Iminopyridine Ligands: Arene Precursors Permit Access to K2-N,N and K3-N,N,S Complexes

10.26434/chemrxiv.9693506.v1 ◽

2019 ◽

Author(s):

Victoria A. Ternes ◽

Hannah A. Morgan ◽

Austin P. Lanquist ◽

Michael P. Murray ◽

Bradley Wile

Keyword(s):

Crystal Structure ◽

Solid State ◽

Strong Field ◽

Active Role ◽

Binding Mode ◽

Phenethyl Alcohol ◽

Ru Complexes

Herein we report the preparation of a series of Ru(II) complexes featuring alpha-iminopyridine ligands bearing thioether functionality (NNSR, where R = Me, CH2Ph, Ph). Metallation using (p cymene)RuCl dimer permits access to (k2-N,N)Ru complexes in which the thioether moiety remains uncoordinated. In the presence of a strong field ligand such as acetonitrile or triphenylphosphine, the p-cymene moiety is displaced, and the ligand adopts a k3-N,N,S binding mode. These complexes are characterized using a combination of solution and solid state methods, including the crystal structure of [(NNSMe)Ru(NCMe)2Cl]Cl. The k2-N,N Ru(II) complexes are shown to serve as efficient precatalysts for the oxidation of sec-phenethyl alcohol at 5 mol% loadings, using a variety of external oxidants and solvents. The complex bearing an S-Ph donor was found to be the most active of those surveyed, suggesting that the thioether donor plays an active role in catalyst speciation for this transformation.

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Relative Reactivities of 1,1,1-Trichloroethane and 1,1,1-Trichlorotrifluoroethane in Competitive Addition Reactions

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19921291 ◽

1992 ◽

Vol 57 (6) ◽

pp. 1291-1298 ◽

Cited By ~ 7

Author(s):

František Adámek ◽

Milan Hájek ◽

Zbyněk Janoušek

Keyword(s):

Free Radical ◽

Reaction Mechanism ◽

Relative Reactivity ◽

Addition Reactions ◽

Radical Initiation ◽

Amine Complexes ◽

Free Radical Initiation ◽

Ru Complexes ◽

Radical Initiators

Relative reactivity of CH3CCl3 and CF3CCl3 measured in competitive addition reactions with 1-hexene in the presence of free radical initiators or Cu, Pd and Ru complexes was found to depend on the type of catalyst. The unusual course of the reaction has been found in the additions catalyzed with copper(I)-amine complexes where CH3CCl3 in competition with CF3CCl3 was completely unreactive. The results have been explained in terms of the change of reaction mechanism and compared with classical free radical initiation.

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