Lu[CH(SiMe3)(2)](3) reacts with [SiO2-700] to give [(equivalent to SiO)Lu[CH(SiMe3)(2)](2)] and CH2(SiMe3)(2). [(equivalent to SiO)Lu[CH(SiMe3)(2)](2)] is characterized by solid-state NMR and EXAFS spectroscopy, which show that secondary Lu center dot center dot center dot C and Lu center dot center dot center dot O interactions, involving a gamma-CH3 and a siloxane bridge, are present. From X-ray crystallographic analysis, the molecular analogues Lu[CH(SiMe3)(2)](3),[O-2,6-tBu-C6H3](x) (x = 0-2) also have secondary Lu center dot center dot center dot C interactions. The H-1 NMR spectrum of Lu[CH(SiMe3)(2)](3) shows that the -SiMe3 groups are equivalent to -125 degrees C and inequivalent below that temperature, Delta G((Te = 148 K))(double dagger) = 7.1 kcal mol(-1). Both -SiMe3 groups in Lu[CH(SiMe3)(2)](3) have (1)J(CH) = 117 +/- 1 Hz at -140 degrees C. The solid-state C-13 CPMAS NMR spectrum at 20 degrees C shows three chemically inequivalent resonances in the area ratio of 4:1:1 (12:3:3); the J-resolved spectra for each resonance give (1)J(CH) = 117 +/- 2 Hz. The Si-29 CPMAS NMR spectrum shows two chemically inequivalent resonances with different values of chemical shift anisotropy. Similar observations are obtained for Lu[CH(SiMe3)(2)](3),[O-2,6-tBu-C6H3](x) (x = 1 and 2). The spectroscopic data point to short Lu center dot center dot center dot C gamma contacts corresponding to 3c-2e Lu center dot center dot center dot C gamma-Si beta interactions, which are supported by DFT calculations. Calculated natural bond orbital (NBO) charges show that C gamma carries a negative charge, while Lu, H gamma, and Si beta carry positive charges; as the number of O-based ligands increases so does the positive charge at Lu, which in turns shortens the Lu center dot center dot center dot C gamma distance. The change in NBO charges and the resulting changes in the spectroscopic and crystallographic properties show how ligands and surface-support sites rearrange to accommodate these changes, consistent with Pauling's electroneutrality concept.