Covalency and Ionicity Do Not Oppose Each Other-Relationship Between Si-O Bond Character and Basicity of Siloxanes

Abstract

Covalency and ionicity are orthogonal rather than antipodal concepts. We demonstrate for the case of siloxane systems [R₃ Si-(O-SiR₂ )_n -O-SiR₃ ] that both covalency and ionicity of the Si-O bonds impact on the basicity of the Si-O-Si linkage. The relationship between the siloxane basicity and the Si-O bond character has been under debate since previous studies have presented conflicting explanations. It has been shown with natural bond orbital methods that increased hyperconjugative interactions of LP(O)→σ*(Si-R) type, that is, increased orbital overlap and hence covalency, are responsible for the low siloxane basicity at large Si-O-Si angles. On the other hand, increased ionicity towards larger Si-O-Si angles has been revealed with real-space bonding indicators. To resolve this ostensible contradiction, we perform a complementary bonding analysis, which combines orbital-space, real-space, and bond-index considerations. We analyze the isolated disiloxane molecule H₃ SiOSiH₃ with varying Si-O-Si angles, and n-membered cyclic siloxane systems Si₂ H₄ O(CH₂ )_n-3 . All methods from quite different realms show that both covalent and ionic interactions increase simultaneously towards larger Si-O-Si angles. In addition, we present highly accurate absolute hydrogen-bond interaction energies of the investigated siloxane molecules with water and silanol as donors. It is found that intermolecular hydrogen bonding is significant at small Si-O-Si angles and weakens as the Si-O-Si angle increases until no stable hydrogen-bond complexes are obtained beyond φ_SiOSi =168°, angles typically displayed by minerals or polymers. The maximum hydrogen-bond interaction energy, which is obtained at an angle of 105°, is 11.05 kJ mol^-1 for the siloxane-water complex and 18.40 kJ mol^-1 for the siloxane-silanol complex.

Keywords: basicity; bonding analysis; covalency; ionicity; quantum chemistry; siloxanes.