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Reduction of 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino] acenaphthene (ArBIG-bian) with an excess of magnesium in tetrahydrofuran (thf) or with an excess of calcium in 1,2-dimethoxyethane (dme) and crystallization of the crude products from the reaction mixtures affords monomeric complexes [(ArBIG-bian)Mg(thf)2] (1) or [(ArBIG-bian)Ca(dme)2] (2), respectively. Hydrolysis of complex 1 affords metal-free diamine [ArBIGbianH2(thf)] (3). Complexes 1 and 2 readily react with CO2 to form the corresponding carbamates [(ArBIG-bian)(CO2)2Mg(thf)2] (4) and [(ArBIG-bian)(CO2)2Ca(dme)2] (5). Compounds 1-5 have been characterized by NMR and IR spectroscopy as well as elemental analysis. The molecular structures of 1, 2, 3, and 5 have been determined by the single crystal X-ray analysis. [ABSTRACT FROM AUTHOR]

Reduction of ArBIG-bian (1, 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with an excess of samarium in tetrahydrofuran (thf) and crystallization of the crude product from a thf/toluene mixture affords [(ArBIG-bian)Sm]·C7H8 (2a), which is free of the coordinating solvent. The use of 1,2-dimethoxyethane (dme) as the reaction medium resulted in the same product, [(ArBIG-bian)Sm]·C4H10O2 (2b), which differs from 2a only in the crystal lattice solvent. Reduction of 1 with an excess of ytterbium in dme gives compound [(ArBIG-bian)Yb(dme)]·2.5C7H8 (3), containing a coordinated dme molecule. All three products consist of dianionic ArBIG-bian ligands whose bulky 2,6-(Ph2CH)2-4-Me–C6H2 groups shield effectively the metal atoms. The newly prepared compounds 2a, 2b and 3 were characterized by 1H NMR and IR spectroscopy. The molecular structures of complexes 2a, 2b and 3 have been established by single crystal X-ray analysis. The intramolecular interactions were analysed on the basis of DFT calculations. The temperature dependence of the magnetic susceptibility of 2b and 3 in the region of 2–300 K was studied. The magnetic moments of complex 2b correspond to divalent samarium. [ABSTRACT FROM AUTHOR]

The reduction of [(dpp-bian)BBr] (1, dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with dilithium naphthalenide in Et2O gives [{(dpp-bian)BBr}Li2(Et2O)2]2 (3). The treatment of [(dpp-bian)BONa] (5) and [(dpp-bian)Ge:] (7) with sodium is accompanied by protonation of the acenaphthylene fragment and affords [{(H-dpp-bian)BONa(dme)2}Na(dme)3] (6) and [(H-dpp-bian)Ge:][Na(dme)3] (8), respectively. Compounds 3, 6 and 8 have been characterized by 1H NMR and IR spectroscopy. The molecular structures of 3, [(dpp-bian)BOK] (4) and 8 have been established by single crystal X-ray analysis. [ABSTRACT FROM AUTHOR]

Molybdenum hexacarbonyl reacts with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (1, dpp-BIAN) and 1,2-bis[(trimethylsilyl)imino]acenaphthene (2, tms-BIAN) in toluene to produce (dpp-BIAN)Mo(CO)4(3) and (tms-BIAN)Mo(CO)4(4), respectively. The reaction of [CpNi(CO)]2with 1yields (dpp-BIAN)NiCp (5). Metathesis between Li2(tms-BIAN) and NiCl2(dppe) affords the Ni(0) complex (tms-BIAN)Ni(dppe) (6). The diamagnetic compounds 3, 4and 6have been characterized by 1H, 29Si and 31P NMR spectroscopy, IR spectroscopy and elemental analysis. The ESR spectrum of the paramagnetic compound 5indicates the presence of Ni(i) coordinated by Cp and a neutral dpp-BIAN ligand. The molecular structures of 3–6have been determined by single-crystal X-ray analysis. [ABSTRACT FROM AUTHOR]

• Bulky aluminum hydrides. • Acenaphthene-1,2-diimine ligands. Insertion of carbon dioxide. The reactions of [(ArBIG-bian)Al(H) 2 Li(THF) 4 ] (1) (ArBIG-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene, THF = tetrahydrofuran), [(dpp-bian)Al(H) 2 Li(THF) 3 ] (2) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) and [(dpp-bian)AlH(Cl)][Na(DME) 3 ] (3) (DME = 1,2-dimethoxyethane) with carbon dioxide proceed with its insertion into Al–H bonds and afford [(ArBIG-bian)Al{μ-OC(H)O} 2 Li(THF) 2 ] (4), [{(dpp-bian)AlOC(H)OLi(THF) 3 } 2 μ-O] (5) and [(dpp-bian)Al(µ-O){µ-OC(H)O}Al(dpp-bian)][Na(DME) 3 ] (6) respectively. Complex 5 is a product of thermally induced transformation of bis-formate intermediate [(dpp-bian)Al{μ-OC(H)O} 2 Li(THF) n ] (5a), which can be isolated from the reaction of 2 and CO 2 at ambient temperature. Newly prepared compounds were characterized by IR and NMR spectroscopy; molecular structures of products 4, 5 and 6 were established by single-crystal X-ray analysis. [ABSTRACT FROM AUTHOR]