Understanding ring strain and ring flexibility in six- and eight-membered cyclic organometallic group 14 oxides

A simple model was developed for the approximation of ring strain energies of homo- and heterometallic, six- and eight-membered cyclic organometallic group 14 oxides and the degree of puckering of their ring conformations. The conformational energy of a ring is modelled as the sum of its angular strain components. The bending potential energy functions for the various endocyclic M-O-M′ and O-M-O linkages (M, M′=Si, Ge, Sn) were calculated at the B3LYP/(v)TZ level of theory using H3MOM′H3 and H2M(OH)2 as model compounds. For the six-membered rings, the minimum total angular contribution to ring strain, ERSGmin was calculated to decrease in the order: cyclo-(H2SiO)3 (13.0 kJ mol−1)>cyclo-H2Sn(OSiH2)2O (7.0 kJ mol−1)>cyclo-H2Ge(OSiH2)2O (4.9 kJ mol−1)>cyclo-H2Si(OSnH2)2O (3.4 kJ mol−1)>cyclo-(H2SnO)3 (1.7 kJ mol−1)>cyclo-H2Si(OGeH2)2O (0.8 kJ mol−1)≈cyclo-H2Ge(OSnH2)2O (0.7 kJ mol−1)>cyclo-H2Sn(OGeH2)2O (0.1 kJ mol−1)≈cyclo-(H2GeO)3 (0 kJ mol−1). All of the six-membered rings were predicted to adopt (nearly) planar conformations (a=0.996