The Chemistry Of Heteroborane Clusters: Molecular Architectures And Beyond

J.Z. DAVALOS; R. NOTARIO; D. HNYK; J. HOLUB; L. LAIN; A. TORRE; D.R. ALCOBA; O.B. OÑA; J.A. SANTABALLA; M. CANLE-L.; J.M. OLIVA

Badajoz

Congreso; 9th Congress on Electronic Structure: Principles and Applications - ESPA 2014; 2014

Universidad de Extremadura

The properties of polyhedral heteroborane clusters, and specially carboranes [1], are emerging as potential tools in materials sciences and biochemical processes [2]. In the last few years we have explored the electronic structure of groundstates [3] and polyradical structures [4] of selected polyhedral heteroboranes. The results to be presented in this congress include the possibility of using one-electron centers in heteroborane complex architectural constructs for mapping Heisenberg spin Hamiltonians [5], and the study, both from the experimental and theoretical point of view, of gas-phase and liquid-phase acidities of a family of (metala)heteroborane clusters [6], as well as the interaction between selected borane clusters and molecules with biochemical interest. Examples of the studied heteroborane clusters are shown in the Figure below: (left) Spin density of an icosahedral ortho-carborane cyclic trimer with Cr atoms, [Cr(1,2-C2B10H10)]3 with high-spin configuration (<S2> = 90) and (right) the superacid closo-CB11H6F6(H) with a computed DeltaGacid = 231.1 kcal/mol using the MP2/6-311+G(d,p) model chemistry, the latter being hundreds of times stronger than fluorosulfuric acid (HFSO3) and over a million times stronger than concentrated sulfuric acid. References: [1] R.N. Grimes in Carboranes, (2nd ed) Academic Press, London (2011); [2] F. Issa, M. Kassiou, L.M. Rendina, Chem. Rev. 111 (2011) 5701; [3] J.M. Oliva, Adv. Quantum Chem. 64 (2012) 105; [4] J.M. Oliva, D.R. Alcoba, L. Lain, A. Torre, Theor. Chem. Acc. 132 (2013) 1329; [5] D.R. Alcoba, A. Torre, L. Lain, O.B. Oña, J.M. Oliva, Int. J. Quantum Chem. (2014), dx.doi.org/10.1002/qua.24698; [6] J.Z. Davalos, J. Gonzalez, R. Ramos, D. Hnyk, J. Holub, J.A. Santaballa, M. Canle-L., J.M. Oliva, J. Phys. Chem. A (2014), dx.doi.org/10.1021/jp412400q