Ab initio and density functional study of structure and bonding of cage compounds containing boron, phosphorus and group 14 atomsElectronic supplementary information (ESI) available: optimized bond lengths and angles. See http://www.rsc.org/suppdata/nj/b3/b301191g/

Abstract

Ab initio and density functional calculations for five vertex cage compounds of the type P2(YB)2EH2, (E=C, Si, Ge, Sn, Y=H, H2N) using 6-311G++(d,p) and 3-21G++(d,p) basis sets, showed that they adopt a trigonal bipyramidal structure of C2v symmetry with the two phosphorus atoms occupying the apical position, the HB or NB groups residing in the trigonal basal plane. The theoretical results agree well with the experimental data for E=Si, Ge and Sn. For the carbon cage P2(HB)2CH2 this structure is a transition state and the minimum is a cage of Cs symmetry with a distorted B–B–C ring in the equatorial plane. Key structural parameters within the cages show a linear dependence on the covalent radii and the diffuseness of the orbitals of the heteroatom E. The results of the natural population analysis (NPA) and the values of nucleus independent chemical shifts (NICS) calculated reveal a bonding description very close to the idealized localized Lewis structure, in contrast to the parent P2(HB)3 cage. This is more pronounced in the case of the NH2 substituted cages.