Our attempts to synthesize the N→Si intramolecularly coordinated organosilanes Ph2L1SiH (1 a), PhL1SiH2 (2 a), Ph2L2SiH (3 a), and PhL2SiH2 (4 a) containing a CHN imine group (in which L1 is the C,N‐chelating ligand {2‐[CHN(C6H3‐2,6‐iPr2)]C6H4}− and L2 is {2‐[CHN(tBu)]C6H4}−) yielded 1‐[2,6‐bis(diisopropyl)phenyl]‐2,2‐diphenyl‐1‐aza‐silole (1), 1‐[2,6‐bis(diisopropyl)phenyl]‐2‐phenyl‐2‐hydrido‐1‐aza‐silole (2), 1‐tert‐butyl‐2,2‐diphenyl‐1‐aza‐silole (3), and 1‐tert‐butyl‐2‐phenyl‐2‐hydrido‐1‐aza‐silole (4), respectively. Isolated organosilicon amides 1–4 are an outcome of the spontaneous hydrosilylation of the CHN imine moiety induced by N→Si intramolecular coordination. Compounds 1–4 were characterized by NMR spectroscopy and X‐ray diffraction analysis. The geometries of organosilanes 1 a–4 a and their corresponding hydrosilylated products 1–4 were optimized and fully characterized at the B3LYP/6‐31++G(d,p) level of theory. The molecular structure determination of 1–3 suggested the presence of a SiN double bond. Natural bond orbital (NBO) analysis, however, shows a very strong donor–acceptor interaction between the lone pair of the nitrogen atom and the formal empty p orbital on the silicon and therefore, the calculations show that the SiN bond is highly polarized pointing to a predominantly zwitterionic Si+N− bond in 1–4. Since compounds 1–4 are hydrosilylated products of 1 a–4 a, the free energies (ΔG298), enthalpies (ΔH298), and entropies (ΔH298) were computed for the hydrosilylation reaction of 1 a–4 a with both B3LYP and B3LYP‐D methods. On the basis of the very negative ΔG298 values, the hydrosilylation reaction is highly exergonic and compounds 1 a–4 a are spontaneously transformed into 1–4 in the absence of a catalyst.