Ferrocene-like iron bis(dicarbollide), [3-Fe-III-(1,2-C2B9H11)(2)](-). The first experimental and theoretical refinement of a paramagnetic B-11 NMR spectrum

0357024 - ÚACH 2011 RIV GB eng J - Journal Article
Pennanen, T. O. - Macháček, Jan - Taubert, S. - Vaara, J. - Hnyk, Drahomír
Ferrocene-like iron bis(dicarbollide), [3-Fe-III-(1,2-C2B9H11)(2)](-). The first experimental and theoretical refinement of a paramagnetic B-11 NMR spectrum.
Physical Chemistry Chemical Physics. Roč. 12, č. 26 (2010), s. 7018-7025. ISSN 1463-9076. E-ISSN 1463-9084
R&D Projects: GA MŠMT LC523; GA ČR GAP208/10/2269
Institutional research plan: CEZ:AV0Z40320502
Keywords : transition-metal-complexes * boron hydride derivatives * correlation-energy
Subject RIV: CA - Inorganic Chemistry
Impact factor: 3.454, year: 2010

Nuclear magnetic resonance (NMR) of paramagnetic molecules (pNMR) provides detailed information on the structure and bonding of metallo-organic systems. The physical mechanisms underlying chemical shifts are considerably more complicated in the presence of unpaired electrons than in the case of diamagnetic compounds. We show that this combined theoretical and experimental analysis constitutes a firm basis for the assignment of experimental B-11 NMR chemical shifts in paramagnetic metallaboranes. In the calculations, the roles of the different physical contributions to the pNMR chemical shift are elaborated, and the performance of different popular exchange-correlation functionals of density-functional theory as well as basis sets, are evaluated. A dynamic correction to the calculated shifts via first-principles molecular dynamics simulations is found to be important. Solvent effects on the chemical shifts were computed and found to be of minor significance.
Permanent Link: http://hdl.handle.net/11104/0195396