The lithium kappa(1)-enamides, Me2NSiMe2CHC(Ph)-{2,6-(R-1)(2)-4-(R-2)C6H2}NLi center dot 3THF (R-1 = Pr-i, R-2 = H L1; R-1 = Et, R-2 = H L2; R-1 = Me, R-2 = H L3; R-1 = R-2 = Me L4; R-1 = Et, R-2 = Me L5), in the presence of titanium tetrachloride, undergo intermolecular rearrangement cyclization reactions resulting in 1,3-migration of the silicon groups and the elimination of dimethylamine affording five examples of bis-azasiliconbridged heterocyclic arylamines, [{2,6-(R-1)(2)-4-(R-2)C6H2}N(Ph)CCSiMe2](2) (R-1 = Pr-i, R-2 = H D1; R-1 = Et, R-2 = H D2; R-1 = Me, R-2 = H D3; R-1 = R-2 = Me D4; R-1 = Et, R-2 = Me D5) in good yield, respectively. The molecular structures of D1-D5 show the two fused N-Si-C-C-C rings to be co-planar indicative of extended pi-conjugation, while their photophysical properties reveal them to be green/blue emitting with high luminescence quantum yields (FF range: 75-99%). Furthermore, the compounds D serve as versatile reactants undergoing ring opening on hydrolysis to afford the saturated 1,4-diimines [{2,6-(R-1)(2)-4-(R-2)C6H2}N(Ph)C-CH2](2) (R-1 = Pr-i, R-2 = H E1; R-1 = Et, R-2 = H E2; R-1 = Me, R-2 = H E3; R-1 = R-2 = Me E4; R-1 = Et, R-2 = Me E5). Alternatively, D can be employed in a redox-promoted cascade reaction to afford the conjugated 1,4-diimines, (E)-[{2,6-(R-1)(2)-4-(R-2)C6H2}NQC(Ph)CH](2) (R-1 = Pr-i, R-2 = H F1; R-1 = Et, R-2 = H F2; R-1 = Me, R-2 = H F3; R-1 = R-2 = Me F4; R-1 = Et, R-2 = Me F5). In addition to D1-D5, E1-E3, E5, F2 and F3 have been the subject of single crystal X-ray diffraction studies.