Zirconium Complexes Supported by an N-Perfluoro-Arylated Diamidopyridyl Ligand: Synthesis of Hydrazinediido Complexes

Abstract

The N-perfluoro-phenylated pyridyldiamine H2N2(PFP)N(py) (1) has been prepared by a palladium-catalyzed coupling of hexafluorobenzene and the diamine (H2NCH2)2C(CH3)(2-C5H4N) using the palladacycle trans-di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl]palladium(II) as catalyst. Reactions of H2N2(PFP)N(py) and Zr(NMe2)4 at room temperature or 90 °C led to the complexes [(N(PFP)N2(TFAP)N(py))ZrF(NMe2)] (2) and [(N2(TFAP)N(py))ZrF2] (3) in which one or two dimethylamido groups replaced one or two ortho fluorine atoms of the pentafluorophenyl groups in the ligand. Reaction of Me3SiX (X = Cl, I) with [(N2(TFAP)N(py))ZrF2] (3) resulted in the formation of mixed halogenated complexes [(N2(TFAP)N(py))ZrFI] (4) and [(N2(TFAP)N(py))ZrFCl] (5) in which the axially bound fluorido ligand is substituted. Reaction of [(N2(TFAP)N(py))ZrF2] (3) with LiNHNPh2 afforded the monohydrazido(1-) complex [(N2(TFAP)N(py))ZrF(NHNPh2)] (6) which was converted to the dimeric fluoro-potassium bridged hydrazinediido complex [Zr(N2(TFAP)N(py))FNNPh2K]2 (7) using KHMDS. The corresponding reaction with LiHMDS yielded the monomeric, donor free complex [Zr(N2(TFAP)N(py))NNPh2] (8).

Supramolecular Perspective of Coordination Effects on Fluorine Interactions

“…In the crystal structure with refcode MINMAZ (fluoro-iodo-( N 2, N 2′-(2-methyl-2-(pyridin-2-yl)­propane-1,3-diyl)­bis­(3,4,5,6-tetrafluoro- N , N -dimethylbenzene-1,2-diaminato))­zirconium­(IV) deuterobenzene solvate), all fluorine atoms that participate in the interactions are bonded to aromatic rings. A comprehensive analysis of the crystal packing has pointed out that all metal complexes are oriented in the way that their aromatic rings are parallel, but without overlapping.…”

“…Model systems for the assessment of the strength of F/F, C–H/F, and C–H/π interactions, extracted from the crystal structure with refcode MINMAZ or obtained by the reduction of their structures, used for the evaluation of coordination effects on the interactions of the fluorine atom bound to the aromatic group.…”

“…Electrostatic potential maps of Zr­(IV) complex, extracted from the crystal structure with refcode MINMAZ (a), amino derivative of tetrafluorobenzene (b), and benzene (c) used for the evaluation of the coordination effects on the interactions of the fluorine atom bound to the aromatic group.…”

“…In the crystal structure with refcode MINMAZ (fluoro-iodo- 22 all fluorine atoms that participate in the interactions are bonded to aromatic rings. A comprehensive analysis of the crystal packing has pointed out that all metal complexes are oriented in the way that their aromatic rings are parallel, but without overlapping.…”

Zirconium and Hafnium Hydrazinediido Half-Sandwich Complexes: Synthesis and Reactivity

“…H NMR (benzene-d 6 , 600.1 MHz, 295 K): δ 8.60 (d, 2 H,3 J H−H = 6.5 Hz, o-NMe 2 C 5 H 4 N), 7.77 (dd, 4 H,3 J H−H = 8.5 Hz,4 J H−H = 1.1 Hz, o-HfNN(C 6 H 5 ) 2 ), 7 25. (s, 2 H, o-C 6 H 3 Me 2 ), 7.21 (t, 4 H, 3 J H−H = 8.5 Hz, m-HfNN(C 6 H 5 ) 2 ), 6.80 (t, 2 H, 3 J H−H = 7.8 Hz, p-HfNN-(C 6 H 5 ) 2 ), 6.63 (s, 1 H, p-C 6 H 3 Me 2 ), 5.74 (d, 2 H, 3 J H−H = 6.8 Hz, m-NMe 2 C 5 H 4 N), 3.56 (dt, 1 H, 2 J H−H = 11.2 Hz, 3 J H−H = 7.1 Hz, CH 2 Na), 3.17 (m, 1 H, CH 2 N-b), 2.58 (dt, 1 H, 2 J H−H = 8.5 Hz, 3 J H−H = 16.3 Hz, CH 2 CNN-a), 2.26 (s, 6 H, C 6 H 3 Me 2 ), 2.22−2.17 (m, 1 H, CH 2 CNN-b), 2.09 (s, 15 H, C 5 Me 5 ), 1.98 (s, 6 H, NMe 2 C 5 H 4 N), 1.97 (broad m, 1 H, CH 2 CH 2 CNN-a), 1.14 (broad m, 1 H, CH 2 CH 2 CNNb) ppm.…”