Titanocene Dichloride Complexes Bonded to Carbosilane Dendrimers Via a Spacer of Variable Length – Molecular Dynamics Calculations and Catalysis of Allylic Coupling Reactions

0423458 - ÚCHP 2014 RIV CH eng J - Journal Article
Strašák, Tomáš - Jaroschik, F. - Malý, M. - Čermák, Jan - Sýkora, Jan - Fajgar, Radek - Karban, Jindřich - Harakat, D.
Titanocene Dichloride Complexes Bonded to Carbosilane Dendrimers Via a Spacer of Variable Length – Molecular Dynamics Calculations and Catalysis of Allylic Coupling Reactions.
Inorganica chimica acta. Roč. 409, SI (2014), s. 137-146. ISSN 0020-1693. E-ISSN 1873-3255
R&D Projects: GA MŠMT(CZ) LC06070
Grant - others:UJEP(CZ) GA13-06989S
Institutional support: RVO:67985858
Keywords : metallodendrimers * titanocene dichloride * allylic homocoupling * molecular dynamics
Subject RIV: CC - Organic Chemistry
Impact factor: 2.046, year: 2014

Carbosilane metallodendrimers of the first and second generation containing 4, 8 or 16 titanocene dichloride endgroups were prepared by the normal hydrosilylation method. Different chain lengths of the carbon spacer between the dendrimer and the Cp linkage were investigated. Computer atomistic models of the second generation metallodendrimers with the length of carbon spacer n = 1, 3 and 5 carbon atoms were created, parametrized, and consequently simulated in THF solvent using molecular dynamics. It was shown that the dendrimers with the longest spacers are the most accessible for reagents, that there is no significant backfolding in those structures and that dynamic Ti-Ti distances are so large, that independent behavior of metallocene parts may be expected. Dendrimers of the second generation with 8 and 16 end groups and the five carbon spacer were used in the catalytic system with manganese metal to efficiently catalyze allylic coupling reactions with low catalyst loadings.
Permanent Link: http://hdl.handle.net/11104/0229744