Perfluoroalkyl-substituted triazapentadienes and their metal complexes.
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.
Siedle
A R
AR
3M Corporate Research Laboratories, St. Paul, Minnesota 55144, USA. arsiedle@mmm.com
Webb
Robert J
RJ
Behr
Fred E
FE
Newmark
Richard A
RA
Weil
David A
DA
Erickson
Kristin
K
Naujok
Roberta
R
Brostrom
Myles
M
Mueller
Mark
M
Chou
Shih-Hung
SH
Young
Victor G
VG