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Synthesis and Reactivity of Ruthenium Phosphite Indenylidene Complexes

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((OPr)-Pr-i)(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((OPr)-Pr-i)(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

We gratefully acknowledge the Royal Society (University Research Fellowship to C.S.J.C.), the EC (CP-FP 211468-2 EUMET and CIG09-GA-2011-293900), the Spanish MINECO (RYC-2009-05226 to A.P.) and the Catalan Government (BE-2011 to A.P.) for funding

© Organometallics, 2012, vol. 31, núm. 21, p. 7415-7426

American Chemical Society

Author: Bantreil, Xavier
Poater Teixidor, Albert
Urbina-Blanco, Cesar A.
Bidal, Yannick D.
Falivene, Laura
Randall, Rebecca A. M.
Cavallo, Luigi
Slawin, Alexandra M. Z.
Cazin, Catherine S. J.
Date: 2012
Abstract: 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((OPr)-Pr-i)(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((OPr)-Pr-i)(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
We gratefully acknowledge the Royal Society (University Research Fellowship to C.S.J.C.), the EC (CP-FP 211468-2 EUMET and CIG09-GA-2011-293900), the Spanish MINECO (RYC-2009-05226 to A.P.) and the Catalan Government (BE-2011 to A.P.) for funding
Format: application/pdf
ISSN: 0276-7333 (versió paper)
1520-6041 (versió electrònica)
Document access: http://hdl.handle.net/10256/8658
Language: eng
Publisher: American Chemical Society
Collection: MICINN/PN 2012-2015/RYC-2009-05226
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/om300703p
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Organometallics, 2012, vol. 31, núm. 21, p. 7415-7426
Rights: Tots els drets reservats
Subject: Ruteni -- Compostos -- Síntesi
Ruthenium compounds -- Synthesis
Catalitzadors
Catalysts
Metàtesi (Química)
Metathesis (Chemistry)
Title: Synthesis and Reactivity of Ruthenium Phosphite Indenylidene Complexes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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