Synthesis and Diverse Transformations of a Dinitrogen Dititanium Hydride Complex Bearing Rigid Acridane‐Based PNP‐Pincer Ligands

Abstract

Studies on N2 activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane‐based acriPNP‐pincer ligands {[(acriPNP)Ti]2(μ2‐η1:η2‐N2)(μ2‐H)2} are presented. This complex enabled N2 cleavage and hydrogenation even without additional H2 or other reducing agents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds such as ZnMe2, MgMe2, AlMe3, B(C6F5)3, PinBH, and PhSiH3 have been well established at the rigid acriPNP‐ligated dititanium framework, such as reversible bonding‐mode change between the end‐on and side‐on/end‐on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry.

Synthesis and Diverse Transformations of a Dinitrogen Dititanium Hydride Complex Bearing Rigid Acridane‐Based PNP‐Pincer Ligands

“…(6), P1ÀN2 1.625-(3). [45] Angewandte Chemie Forschungsartikel results demonstrate again the significant effects of the rigid acri PNP-pincer ligands.…”

“…Selected bond lengths []: Ti1ÀN1 2.107(3), Ti1ÀN2 2.002(4), Ti2ÀN1 2.037(3), Ti2ÀN2 2.064(3), Ti1ÀTi2 2.565 (7), N1ÀB1 1.427(5), N2ÀB2 1.415 (5). [45] Scheme 7. Reaction of complex 2 with phenylsilane.…”

“…X-ray crystal structure of 12,with ellipsoids at 50 %p robability.Hydrogen atoms (except H1, H2, H3, and H4) and the i Pr groups are omitted for clarity.S elected bond lengths []: Ti1ÀN1 2.080(2), Ti1ÀN2 2.108(2), Ti2ÀN2 1.838(2), Si1ÀN1 1.691(2), Si2ÀN1 1.712(2), Si2ÀN2 1.725(2). [45] Scheme 8. Formation of acyclodisilylenediazane Unit.…”

“…Ti-m 2 -h 1 :h 2 -N 2 N imide N nitride 2- 15 [45] transformation was accompanied by H 2 release as monitored by the 1 HNMR spectroscopy in C 6 D 6 .T he 15 NN MR spectrum of 3-15 N showed ad oublet at d = À73.48 (J N-P = 30.8 Hz) and as inglet at d = 544.75, which are assignable to the phosphinimide and nitride units,respectively (Table 1). An X-ray diffraction analysis revealed that 3 possesses aT im etallacyclopropane with the Ti1 À C1, Ti1 À C2 and C1 À C2 bond distances of 2.254(4), 2.137(3) and 1.474(6) , respectively ( Figure 2).…”

“…Ther eaction of 2 with B(C 6 F 5 ) 3 in diethyl ether occurred rapidly at room temperature,affording the corresponding N 2 - (2), Ti1ÀC1 2.140(2), Al1ÀN1 1.930(2), Al1'ÀN1 1.942(2);N 1-Al1-N1' 89.30 (8), Al1-N1-Al1' 90.70 (8). [45] Figure 6. X-ray crystal structure of 8,with ellipsoids at 50 %p robability.Hydrogen atoms (except H1 and H2) and the i Pr groups are omitted for clarity.S elected bond lengths []: Ti1ÀN1 1.916(2), Ti1ÀN2 2.072(2), Ti2ÀN2 1.821(2), N1ÀN2 1.339(3), Al1ÀN1 1.982(2).…”