Fluxional behavior of the dinitrogen ligand 2,9-dimethyl-1,10-phenanthroline in cationic methyl platinum(II)...

The ionic methylplatinum(II) complexes [Pt(Me)(L)(dmphen)]X (dmphen = 2,9-dimethyl-1,10-phenanthroline, L = Me(2)SO, X = PF(6)(-) 1a, BF(4)(-) 1b, CF(3)SO(3)(-) 1c, ClO(4)(-) 1d, B(C(6)H(5))(4)(-) 1e, [B(3,5-(CF(3))(2)C(6)H(3))(4)](-) 1f; L = n-Bu(2)SO, X = CF(3)SO(3)(-) 1g; L = PPh(3), X = PF(6)(-) 2a, BF(4)(-) 2b, CF(3)SO(3)(-) 2c, ClO(4)(-) 2d, B(C(6)H(5))(4)(-) 2e, [B(3,5-(CF(3))(2)C(6)H(3))(4)](-) 2f; X = CF(3)SO(3)(-), L = CyNH(2) 3a, i-PrNH(2) 3b, 2,6-Me(2)py 3c, EtNH(2) 3d, AsPh(3) 3e, dimethylthiourea (Me(2)th) 3f and the uncharged [Pt(Me)(X)(dmphen)] (X = SCN(-) 4a, SeCN(-) 4b) complexes have been synthesized and fully characterized. In chloroform, as well as in acetone or methanol, complexes 1a-1g, 2a-2h (X = Cl(-) g, NO(2)(-) h, formed "in situ"), and 3e show dynamic behavior due to the oscillation of the symmetric chelating ligand dmphen between nonequivalent bidentate modes. All the other compounds feature a static structure in solution. The crystal structure of 2a shows a tetrahedral distortion of the square planar coordination geometry, a loss of planarity of the dmphen ligand, and, most notably, a rotation of the dmphen moiety, around the N1-N2 vector, to form a dihedral angle of 42.64(8) degrees with the mean coordination plane. The hexafluorophosphate ion lies on the side of the phenanthroline ligand. The interionic structures of 2a, 2b, and 2f were investigated in CDCl(3) at low temperature by (1)H-NOESY and (19)F[(1)H]-HOESY NMR spectroscopies. Whereas PF(6)(-) (2a) and BF(4)(-) (2b) show strong contacts with the cation [Pt(Me)(PPh(3))(dmphen)](+), being located preferentially on the side of the phenanthroline ligand, the [B(3,5-(CF(3))(2)C(6)H(3))(4)](-) (2f) ion does not form a tight ion pair. The dynamic process was studied by variable-temperature NMR spectroscopy for 1a-1f and 2a-2h in CDCl(3). The activation energies DeltaG(298) for the sulfoxide complexes 1a-1f are lower than those of the corresponding phosphine complexes 2a-2f by approximately 10 kJ mol(-)(1). The nature of the counteranion exerts a tangible influence on the fluxionality of dmphen in both series of complexes 1 and 2. The sequence of energies observed for 2a-2h encompasses an overall difference of about 16 kJ mol(-)(1), increasing in the order Cl(-) approximately NO(2)(-) << CF(3)SO(3)(-) < ClO(4)(-) < B(C(6)H(5))(4)(-) < BF(4)(-) approximately PF(6)(-) < B(3,5-(CF(3))(2)C(6)H(3))(4)(-). Acetone and methanol have an accelerating effect on the flipping. Concentration-dependent measurements, carried out in CDCl(3) for 2a with n-Bu(4)NPF(6) and the ligands dmphen, n-Bu(2)SO, sec-Bu(2)SO, and sec-Bu(2)S showed that the rate of the fluxional motion is unaffected by added n-Bu(4)NPF(6), whereas in the other cases this increases linearly with increasing ligand concentration, according to a pattern of behavior typical of substitution reactions. Dissociative and associative mechanisms can be envisaged for the observed process of flipping. Dissociation can be prevalent within the ion pair formed by a "noncoordinating" anion with the metallic cationic complex in chloroform. Among the possible associative mechanisms, promoted by polar solvents or by relatively strong nucleophiles, a consecutive displacement mechanism is preferred to intramolecular rearrangements of five-coordinate intermediates.