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Hetero-multimetallic Catalysts

#G-1361


Hetero-Multimetallic Catalysts for the Asymmetric Formation of C-C Bonds

Tech Area / Field

  • CHE-SYN/Basic and Synthetic Chemistry/Chemistry

Status
8 Project completed

Registration date
08.11.2005

Completion date
17.03.2011

Senior Project Manager
Mitina L M

Leading Institute
Tbilisi State University, Georgia, Tbilisi

Supporting institutes

  • INEOS (Organo-Element Compounds), Russia, Moscow

Collaborators

  • University of Oxford / Chemical Research Laboratory, UK, Oxford\nUniversite de Paris-Sud / Institut de Chimie Moleculaire et des Materiaux D’Orsay, France, Orsay\nSolvias AG, Switzerland, Basel\nUniversity of Newcastle / School of Natural Sciences, UK, Newcastle upon Tyne\nUmicore AG & Co.KG , Precious metals chemistry, Germany, Hanau

Project summary

Research Objectives

The primary scientific objective of this proposal is the design and creation of a novel family of catalysts (including chiral versions) based on multinuclear complexes of metals. The project target is creation of catalysts superior to those based on mononuclear complexes of the same metals. This objective can be broken down into sub-objectives as detailed below:

Sub-objective 1: The elaboration of conceptually novel bimetallic pincer complexes based on ferrocene- and ruthenocene P,C,P complexes of palladium and platinum - catalysts for carbon-carbon coupling reactions, such as Michael addition, Aldol addition and C-allylation reactions (including chiral versions).

Sub-objective 2: Synthesis and characterization of Pd(II) or/and Cu(I) complexes by the reactions of [CuX] (X = CF3SO3, J, Br, H, OtBu) with 1,1'-bis(phosphino)metallocenes. The complexes obtained in these reactions will be tested as catalysts of Michael addition, Aldol addition and C-allylation reactions (including chiral versions).

Sub-objective 3: Synthesis and structural characterization of bimetallic chiral complexes formed in situ from two chiral complexes of metals. Such complexes will include systems derived from negatively and positively charged complexes of different metal ions [starting with Ti(IV), Co(III) and V(V)], including those capable of forming oxygen bridges between the two metals (the most often encountered motif among metallo-enzymes), and chiral Schiff complexes connected by conformationally labile covalent bridges. The complexes will be studied as catalysts of asymmetric C-C bond formation reactions such as Michael addition, TMSCN addition to aldehydes and Aldol addition.

Sub-objective 4: Synthesis and elaboration of novel trinuclear catalysts based on positively charged achiral metallocene bimetallic complexes (see above), where chiral counter-anion section will be represented by negatively charged enatiomerically pure octahedral stereochemically inert complexes of Co(III). Asymmetic catalysis of Michael and Aldol additions by the trinuclear complexes is being planned.

As a result of the endeavour, novel approach to the design and synthesis of efficient multinuclear metal catalysts of asymmetric C-C bond formation reaction will be elaborated.


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