Download PDF by Friend J.N. (ed.): A Textbook of Inorganic Chemistry

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The pyridine group is in an equatorial disposition on the metallacycle ring with minor steric hindrance. Fluxional behaviour of complexes 2 and 4 The fluxional behaviour of complexes 2 and 4 was studied both in acetone-d6 and in 1,1' ,2,2' -tetrachloroethane-d2 . These solvents were selected due to the difference in their coordination ability and to the temperature range of their liquid state, which allowed a complementary NMR study to be undertaken. The dynamic process involves the interconversion of the cis and trans stereoisomers.

This aspect was also addressed by Pilloni et ai. in their electrochemical studies of complex 2 [Ic]. In order to clarify this point, DFT calculations [6] (ADF program [IOD were performed on a model of [(dppf)Cu(/-L-Cl)zCu(dppf)] where the phenyl groups were replaced by hydrogen atoms. Complex 2 was also tried, but it exceeded our possibilities and could not be handled. The geometry of model 3 was fully optimized without symmetry constraints and found to be in good agreement with the X-ray determined structure.

Acknowledgments This work was supported by PRAXIS XXI under project PRAXIS/PCNAlC/QUUlO3/96. We thank Z. M. Tavares for the elemental analysis (ITQB) and cyclic voltammetric experiments. P. Pinto thanks ITQB for a grant. M. J. Calhorda, P. Pinto, and V. Felix thank the TMR Transition Metal Clusters in Catalysis and Organic Synthesis. The University of Reading and EPSRC are thanked for funds for the Image Plate system. References [1] a) Pilloni G, Graziani R, Longato B, Corain B (1991) Inorg Chim Acta 190: 165; b) Pilloni G, Corain B, Degano M, Longato B, Zanotti G (1993) J Chern Soc Dalton Trans 165; c) Pilloni G, Longato B (1993) Inorg Chim Acta 208: 17; d) Pilloni G, Valle G, Corvaja C, Longato B, Corain B (1995) Inorg Chern 34: 59lO; e) Pilloni G, Longato B, Bandoli G, Corain B (1997) J Chern Soc Dalton Trans 819; f) Diez J, Gamasa MP, Gimeno J, Aguirre A, Garcia-Grande S (1999) Polynuclear Cu(l)dppj Complexes [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] 41 Organornetallics 18: 662; h) Pilloni G, Corain B, Degano M, Longato B, Zanotti G (1993) J Chern Soc Dalton Trans 1777; i) Pilloni G, Longato B, Corain B (1991) 420: 57 Frausto da Silva HR, Williams RJP (1991) The Biological Chemistry of the Elements.

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