Here we report that attempted preparation of low-valent CaI complexes in the form of LCa-CaL (where L is a bulky β-diketiminate ligand) under dinitrogen (N2) atmosphere led to isolation of LCa(N2)CaL, which was characterized crystallographically. The N22ˉ anion in this complex reacted in most cases as a very potent two-electron donor. Therefore, LCa(N2)CaL acts as a synthon for the low-valent CaI complex LCa-CaL, which was the target of our studies. The N22ˉ anion could also be protonated to diazene (N2H2) that disproportionated to hydrazine and N2. The role of Ca d orbitals for N2 activation is discussed.

The steric bulk of the well‐known DIPPBDI ligand (CH[C(CH3)N‐DIPP]2, DIPP=2,6‐diisopropylphenyl) was increased by replacing isopropyl for isopentyl groups. This very bulky DIPePBDI ligand could not stabilize the radical species (DIPePBDI)Mg.: reduction of (DIPePBDI)MgI with Na gave (DIPePBDI)2Mg2 with a rather long Mg‐Mg bond of 3.0513(8) Å. Addition of TMEDA prior to reduction gave complex (DIPePBDI)2Mg2(C6H6), which could also be obtained as its THF adduct. It is speculated that combination of a bulky spectator ligand and TMEDA prevents dimerization of the intermediate MgI radical, which then reacts with the benzene solvent. Complex (DIPePBDI)2Mg2(C6H6), which formally contains the anti‐aromatic anion C6H62−, reacted with tBuOH as a Brønsted base to 1,3‐ and 1,4‐cyclohexadiene and with H2 as a two electron donor to (DIPePBDI)2Mg2H2 and C6H6. It also reductively cleaved the C−F bond in fluorobenzene and gave (DIPePBDI)MgPh, (DIPePBDI)MgF, and C6H6.

Key to the isolation of the first alkyl strontium complex was the synthesis of a strontium hydride complex that is stable towards ligand exchange reactions. This goal was achieved by using the super bulky β‐diketiminate ligand DIPePBDI (CH[C(Me)N‐DIPeP]2, DIPeP=2,6‐diisopentylphenyl). Reaction of DIPePBDI‐H with Sr[N(SiMe3)2]2 gave (DIPePBDI)SrN(SiMe3)2, which was converted with PhSiH3 into [(DIPePBDI)SrH]2. Dissolved in C6D6, the strontium hydride complex is stable up to 70 °C. At 60 °C, H–D isotope exchange gave full conversion into [(DIPePBDI)SrD]2 and C6D5H. Since H–D exchange with D2 is facile, the strontium hydride complex served as a catalyst for the deuteration of C6H6 by D2. Reaction of [(DIPePBDI)SrH]2 with ethylene gave [(DIPePBDI)SrEt]2. The high reactivity of this alkyl strontium complex is demonstrated by facile ethylene polymerization and nucleophilic aromatic substitution with C6D6, giving alkylated aromatic products and [(DIPePBDI)SrD]2.

Scheme 16. Synergistic reactions between K and Al: a) (DIPP BDI)Al reduces in the presence of KHMDS/benzene at the 1,4-positions. b) Reaction of aluminoxane [K{Al(NON Dipp)(O)}] 2 (19) with 1 atm CO. Scheme 15. Synthesis of (Si NON)AlI, [KAl(Si NON)] 2 (15) and [K{Al(Si NON)(COT)}] 1 (16).

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