Perfluoroalkyl-Substituted Triazapentadienes and Their Metal Complexes

Abstract

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.

PdII‐Promoted Single‐Pot Template Transformations of Benzonitriles, Cyanoguanidine and Sodium Dicyanamide with the Formation of Symmetrical and Asymmetrical (1,3,5‐Triazapentadienate)palladium(II) Complexes

“…[3,5,6,12] These pre-prepared tap ligands usually contain N 1 ,N 3 nitrogen atoms connected to bulky groups, e.g. phenyls, and can be synthesized by the reaction of primary amines, RNH 2 , with the fluorinated imine C 3 F 7 -CF=N-C 4 F 9 [6] or by the Ley and Muller method [23] where amidine is treated with an N-imidoyl chloride.…”

“…[3,5,6,12] These pre-prepared tap ligands usually contain N 1 ,N 3 nitrogen atoms connected to bulky groups, e.g. phenyls, and can be synthesized by the reaction of primary amines, RNH 2 , with the fluorinated imine C 3 F 7 -CF=N-C 4 F 9 [6] or by the Ley and Muller method [23] where amidine is treated with an N-imidoyl chloride. [3][4][5]12] Another route to tap-Pd complexes involves template transformations of cyanopyridines [10,16] through lithium amidinate, which is produced in situ from LiN(SiMe 3 ) 2 [10] or via an oxime-mediated process.…”

“…[17][18][19][20] Until now only copper, nickel and platinum ions have been studied in these transformation reactions and no data on palladium(II)-mediated transformations have been reported, irrespective of the potential ability of Pd II to form tap complexes [3,5,6,10,12,16] and its expected behavioural similarity to that of Pt II in promoting nucleophilic addition reactions with substrates containing the CϵN group, namely organonitriles. [24][25][26][27] Thus, one can conclude that the template conversions of CϵN-containing reagents to tap ligands bound to Pd II cen-ters deserve to be explored further as a convenient route to new tap-palladium(II) complexes.…”

Synthesis of Secondary, Tertiary and Quaternary 1,3,5‐Triazapenta‐1,3‐dienes and Their CoII, ZnII, PdII, CuII and BF2 Coordination Compounds

“…dienes 3 were first synthesized by Cooper, Partridge, Oxley and Short using various reaction paths. [6,7] The synthesis of tertiary perfluoroalkyl-triazapentadienes was achieved by Siedle et al in 2003. [8] Quaternary 1,3,5-triazapenta-1,3-dienes 4 have rarely been reported.…”

“…[6,7] The synthesis of tertiary perfluoroalkyl-triazapentadienes was achieved by Siedle et al in 2003. [8] Quaternary 1,3,5-triazapenta-1,3-dienes 4 have rarely been reported. By methylation of 3 Cooper, Partridge and Short obtained such a penta-substituted example.…”