Issue 37, 2011
From the journal:

Dalton Transactions

Coordination to metal centers: A tool to fix high energy conformations in organic molecules. Application to 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and related macrocycles

J. Pérez,a   R. Carrascosa,a   L. García,a   G. Barandika,b   A. Calderón-Casado,c   E. Pérez,a   J. L. Serranoa  and  M. D. Santanad  

a Dpto. Ingeniería Minera, Geológica y Cartográfica (Área de Química Inorgánica), Universidad Politécnica de Cartagena, 30203 Cartagena (Murcia), Spain
E-mail: jose.pperez@upct.es
Fax: +34 968325420
Tel: +34 968326420

b Dpto. Química Inorgánica, Facultad de Farmacia, UPV/EHU. Paseo de la Universidad, 7. 01006 Vitoria-Gasteiz, Spain

c Dpto. Mineralogía y Petrología, Facultad de Ciencia y Tecnología, UPV/EHU. Apdo 644, 48080 Bilbao, Spain

d Dpto. Química Inorgánica., Universidad de Murcia, 30071 Murcia, Spain

Abstract

The solid state conformational preferences of ligand 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene (L1) and its 9-methyl derivative (L2) in transition metal complexes have been determined by a probabilistic method using data retrieved from the Cambridge Structural Database. These macrocyclic compounds, as ligands, tend to adopt a preferential conformation (85% of cases). The ring containing the C=N bond adopts a distorted half-chair conformation, the ring defined by both the N-sp3 shows a distorted envelope conformation, and the remaining ring exhibits a chair conformation. This conformation corresponds to the enantiomer pair RN5SN9SP/SN5RN9RP. Molecular mechanics calculations demonstrate that this is a high energy conformation for the organic molecule, far from the energy minimum. Two other enantiomer pairs are observed in experimental structures. The influence of the coordination on the conformation of the organic ligands has been studied by DFT calculations, and a clear correlation with the geometry of the coordination sphere has been found.

Graphical abstract: Coordination to metal centers: A tool to fix high energy conformations in organic molecules. Application to 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and related macrocycles

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Article information

DOI
https://doi.org/10.1039/C1DT11281C
Article type
Paper
Submitted
05 Jul 2011
Accepted
18 Jul 2011
First published
18 Aug 2011

Dalton Trans., 2011,40, 9504-9511

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Coordination to metal centers: A tool to fix high energy conformations in organic molecules. Application to 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and related macrocycles

J. Pérez, R. Carrascosa, L. García, G. Barandika, A. Calderón-Casado, E. Pérez, J. L. Serrano and M. D. Santana, Dalton Trans., 2011, 40, 9504 DOI: 10.1039/C1DT11281C

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