%0 Journal Article
%A Bantreil, Xavier
%A Poater, Albert
%A Urbina-Blanco, César
A.
%A Bidal, Yannick D.
%A Falivene, Laura
%A A. M. Randall, Rebecca
%A Cavallo, Luigi
%A M. Z. Slawin, Alexandra
%A S. J. Cazin, Catherine
%D 2012
%T Synthesis and Reactivity
of Ruthenium Phosphite Indenylidene
Complexes
%U https://acs.figshare.com/articles/journal_contribution/Synthesis_and_Reactivity_of_Ruthenium_Phosphite_Indenylidene_Complexes/2470288
%R 10.1021/om300703p.s001
%2 https://acs.figshare.com/ndownloader/files/4112989
%K metathesi
%K catalyst loadings
%K Ruthenium Phosphite Indenylidene ComplexesThe synthesis
%K precatalyst
%K NHC ligands
%K cis complexes
%K cis configuration
%K NMR experiments
%K trans counterparts
%K phosphite
%X The synthesis of the four olefin metathesis precatalysts Caz-1a–d, featuring the NHC ligand N,N′-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene
(SIMes) and four different phosphites (P(OiPr)3, P(OPh)3, P(OEt)3, and P(OMe)3), is reported. The complexes are readily synthesized from
commercially available [RuCl2(3-phenylinden-1-ylidene)(pyridine)(SIMes)]
(Ind-III) in yields of up to 88%. These complexes adopt
an unusual cis configuration between the phosphite and the NHC ligands.
NMR experiments and computational studies confirm that the cis complexes
are thermodynamically favored in comparison to their trans counterparts.
In addition, the isomerization from trans to cis occurs via a mononuclear
and non-dissociative mechanism. Among the four precatalysts, cis-Caz-1a, featuring a P(OiPr)3 ligand, displays the highest activity in ring-closing
metathesis and cross-metathesis transformations. Experiments at low
catalyst loadings demonstrated the potential of this catalyst, allowing
better conversions than with commonly used commercially available
precatalysts.
%I ACS Publications