The reactions of azide ions coordinated to ruthenium(II) centers bearing two 2,2′-bipyridine (bpy) ligands, that is, Br) afforded imine (NH=CR 1 R 2 ) and ammine (NH 3 ) ligands with dinitrogen evolution. The formation of these nitrogen-containing moieties depended on both the reaction solvent and the alkyl group of the haloalkane. Four types of imine complexes, [a] Measurements: Elemental analyses were performed with a Perkin-Elmer 2400-II instrument. The FAB MS spectra were measured with a JEOL JMS-700 spectrometer with m-nitrobenzyl alcohol as the matrix. The 1 H and 13 C NMR spectra were obtained with JEOL JML-AL500 and AL300 spectrometers. The UV/Vis spectra were obtained with a Shimadzu MultiSpec-1500 diode array spectrophotometer. The IR spectra were recorded with a Perkin-Elmer FT-2000 FTIR spectrophotometer with samples prepared as KBr disks. The GC was performed with a Shimadzu GC-8A instrument with an MS13X column. The GC-MS was performed with a JEOL Automass SYSTEM II instrument. The electrochemical measurements were performed with CH 3 CN solutions containing 0.1 mol dm -3 tetraethylammonium perchlorate (TEAP, Nakarai Tesque Ltd.) and CH 3 NO 2 solutions containing 0.1 mol dm -3 tetra-n-butylammonium perchlorate (TBAP, Nakarai Tesque Ltd.) as the supporting electrolyte with a platinum disk working electrode (φ = 1.6 mm) and an Ag/0.01 mol dm -3 AgNO 3 reference electrode with a BAS 100B/W electrochemical analyzer. At the end of each measurement, ferrocene was added as an internal standard to correct the redox potentials.DFT Calculations: All calculations were performed with the Gaussian 09 program. [28] The geometry optimizations were performed at the B3LYP level of density functional theory with the Los Alamos effective core potential plus DZ (LANL2DZ) and cc-pVDZ basis sets.
Materials: RuCl 3 ·nH 2 O (Ru content 40.11 wt.-%) was purchased from Furuya Kinzoku Inc. [Ru II Cl 2 (bpy) 2 ]·2H 2 O, [Ru(N 3 ) 2 (bpy) 2 ]·H 2 O (1·H 2 O), [Ru II (NH 3 ) 2 (bpy) 2 ][PF 6 ] 2 , and [Ru II (NH=CH 2 )(NCCH 3 )(bpy) 2 ]-[PF 6 ] 2 were prepared by the reported procedures. [16,25,29] Caution! Sodium azide is potentially explosive and should be handled with care.
