Abstract: | The 13C-NMR. spectra of the series of complexes η6-naphthalene · CrL3 (L? CO ( 1 ), PF3 ( 2 ), PF2OMe ( 6 ), P(OMe)3 ( 3 ), C10H8 (= 3 L) ( 4 ) and PMe3 ( 5 )) are reported. Definite assignments of the 13C-NMR. resonances were made through the synthesis of 2, 3, 6, 7-2H4]-naphthalene complexes. The coordinated ring 13C-resonance are found to undergo a smooth transition to higher field with increasing donor character of the coligands L. A correlation of the coordination shifts with the reactivity of the coordinated naphthalene is proposed. In complexes containing strong acceptor ligands the naphthalene is activated to attack by nucleophiles. Sequential treatment of complexes 1–4 , 6 and C10H8FeC5H5]+PF6]? ( 7 ) with stabilized carbanions and I2 or Ce(IV)-salt yields α-substituted naphthalenes in the case of 1 , 2 , 6 and 7 but not in the case of 3 and 4 . Treatment of 3 with an excess of HBF4 results not in the expected metal protonation but in a novel ligand transformation to yield 6 . |