Triazapentadienides, C(3)F(7)-C(=NR)-N=C(NHR)-C(3)F(7), result from the reaction of primary amines RNH(2) with the fluorinated imine C(3)F(7)-CF=N-C(4)F(9). The aniline derivative (R = Ph) is a weak monoprotic acid in dmso. Its conjugate base exhibits an extensive coordination chemistry. It acts as a bidentate ligand toward the molecular fragments Pd(C(3)H(5)), Rh(c-C(8)H(12)), Ir(c-C(8)H(12)), and Rh(CO)(2). The chelates [C(3)F(7)-C(NPh)-N-C(NPh)-C(3)F(7)](2)M, M = Mg, Mn, Fe, Co, Ni, Cu, Zn, and Pd, were prepared. In the crystallographically characterized Co complex, the metal is 3d(7), S = (3)/(2) and tetrahedrally coordinated. Spin densities at carbon in the C(6)H(5) and C(3)F(7) groups were estimated from the (1)H and (19)F contact shifts. Spin delocalization onto phenyl sp(2) carbons is approximately 10 times greater than onto the fluorinated sp(3) carbons.
The compound [Ph2N3C2(C3F7)2]HgCH3 was synthesized from Na[Ph2N3C2(C3F7)2] and CH3HgCl. In solution, it exists as a mixture of two isomers that interconvert slowly on the NMR
time scale. Both isomers feature a η1-Ph2N3C2(C3F7)2 ligand. In the asymmetrical one, the
CH3Hg group is bonded to one of the two terminal nitrogen atoms. In the more stable
symmetrical isomer, [PhNC(C3F7)]2NHgCH3, mercury is attached to the central nitrogen
atom. It is this isomer that crystallizes and that was characterized by X-ray diffraction.
Thermodynamic parameters for the CH3Hg shift reaction were obtained by DNMR
spectroscopy. 19F NMR spectra were analyzed. A metallotropic rearrangement was not
observed in [Ph2N3C2(C3F7)2]AuPPh3.
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