A chelating tetrapeptide rhodium complex comprised of a histidylidene residue: biochemical tailoring of an NHC-Rh hydrosilylation catalyst.

نویسندگان

  • Angèle Monney
  • Martin Albrecht
چکیده

Coupling of a histidinium salt with a MetAlaAla amino acid sequence followed by metallation with [RhCl(cod)](2) yields a rhodium(I) NHC complex with a pending peptide residue. Methionine chelation, induced by chloride abstraction from the metal coordination sphere, affords an efficient hydrosilylation catalyst precursor comprised of a peptidic macrocyclic chelate backbone.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Peptide-tethered monodentate and chelating histidylidene metal complexes: synthesis and application in catalytic hydrosilylation.

The Nδ,Nε-dimethylated histidinium salt (His*) was tethered to oligopeptides and metallated to form Ir(III) and Rh(I) NHC complexes. Peptide-based histidylidene complexes containing only alanine, Ala-Ala-His*-[M] and Ala-Ala-Ala-His*-[M] were synthesised ([M] = Rh(cod)Cl, Ir(Cp*)Cl2), as well as oligopeptide complexes featuring a potentially chelating methionine and tyrosine residue, Met-Ala-Al...

متن کامل

Stereospecific synthesis and catalytic activity of L-histidylidene metal complexes.

We report on the synthesis, metal coordination, and catalytic impact of histidylidene, a histidine-derived N-heterocyclic carbene (NHC) ligand. The histidinium salt 3, comprising methyl substituents at both heterocyclic nitrogens and protected at the C- and N-terminus of the amino acid, was rhodated and iridated by a transmetallation protocol using Ag(2)O. Ambient temperature and short reaction...

متن کامل

Heterogeneous catalysts based on supported Rh–NHC complexes: synthesis of high molecular weight poly(silyl ether)s by catalytic hydrosilylation†‡

The new rhodium(I) complexes [Rh(Cl)(COD)(R-NHC-(CH2)3Si(O Pr3)3)] (R = 2,6-diisopropylphenyl (2a); n-butyl (2b)) have been synthesised and fully characterised. The study of their application as ketone hydrosilylation catalysts showed a clear N-substituent effect, 2a being the most active catalyst precursor. Complex 2a has been immobilised in the mesoporous materials MCM-41 and KIT-6. The new h...

متن کامل

Tandem deuteration/hydrosilylation reactions catalyzed by a rhodium carbene complex under solvent-free conditions.

The complex [Rh(I(t)Bu)(2)HCl] has been shown to be an active catalyst in the hydrosilylation of carbonyl and imine complexes. This reactivity, combined with the previously reported H/D exchange catalyzed by these complexes allows for a one pot, two step reaction using a single catalyst for both H/D exchange and hydrosilylation. Using triethylsilane, [Rh(I(t)Bu)(2)Cl] catalyst, and D(2) gas, de...

متن کامل

Selective rearrangement of terminal epoxides into methylketones catalysed by a nucleophilic rhodium-NHC-pincer complex.

An efficient Rh(I)-NHC-pincer catalyst for the highly regioselective Meinwald rearrangement of monoalkylated epoxides into methylketones under mild conditions is presented. The nucleophilic epoxide opening is assisted by Lewis acids.

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Chemical communications

دوره 48 89  شماره 

صفحات  -

تاریخ انتشار 2012