468058-88-0

Upstream product

• 1217358-40-1 [{(DippNacnac)CaI(OEt₂)}2] 
• 60-29-7 diethyl ether 
• 205993-24-4 potassium N,N′-bis(2,6-diisopropylphenyl)pentane-2,4-diiminate 

Relevant academic research and scientific papers

Dehydrohalogenation of halobenzenes and C(sp3)-X (X = F, OPh) bond activation by a molecular calcium hydride

The molecular calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2), effects the slow hydrodehalogenation of C6H5X (X = I, Br) to provide benzene and the respective dimeric calcium halides, [(BDI)CaX]2. Although a similar reaction with fluorobenzene was non-discriminating, the analogous hydrogenation of chlorobenzene was observed, albeit this process yields the calcium hydride-chloride as the alkaline earth-containing product. Assessment of the bromide- and chloride-based processes by density functional theory (DFT) calculations, imply that the reactions take place with the retention of the dimeric calcium structures throughout. Both systems invoke an SNAr-type displacement of the halide, via barriers (in the range 32–34 kcal mol?1 for C6H5Br and 31.1–32.9 kcal mol?1 for C6H5Cl), which vary only marginally during the transformation of the initial hydride and halide-hydride intermediates. The isolation of the calcium hydride-chloride is ascribed, therefore, to its more rapid crystallisation and depletion from solution. Also reported is the reactivity of [(BDI)CaH]2 with α,α,α-trifluorotoluene and anisole, which yield the corresponding dicalcium hydride-fluoride and phenoxide derivatives, respectively, rather than the products of directed ortho metalation.

Calcium Hydride Catalyzed Highly 1,2-Selective Pyridine Hydrosilylation

Reaction of the calcium hydride complex (DIPPnacnac-CaH·THF)2 with pyridine is much faster and selective than that of the corresponding magnesium hydride complex (DIPPnacnac = [(2,6-iPr2C6H3)NC(Me)]2C

Multimetallic Alkaline-Earth Hydride Cations

Reactions of dimeric β-diketiminato (BDI) magnesium and calcium hydrides with [(BDI)Mg]+[Al{OC(CF3)3}4]- provide ionic multimetallic hydride derivatives, which have been characterized by single-crysta

β-Diketiminate-Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies

The preparation and characterization of a series of magnesium(II) iodide complexes incorporating β-diketiminate ligands of varying steric bulk and denticity, namely, [(ArNC-Me)2CH]- (Ar = phenyl, (PhNacnac), mesityl (MesNacnac), or 2,6-diisopropyl-phenyl (Dipp, DippNacnac)), [(DippNC-tBu) 2CH]- (tBuNacnac), and [(DippNC-Me)(Me2NCH 2CH2NCMe)CH]- (DmedaNacnac) are reported. The complexes [(PhNacnac)MgI(OEt2)], [(MesNacnac)MgI(OEt2)], [(DmedaNacnac)MgI(OEt2)], [(MesNacnac)MgI-(thf)], [(DippNacnac)MgI(thf)], [(tBuNac-nac)MgI], and [(tBuNacnac)MgI-(DMAP)] (DMAP = 4-dimethylamino-pyridine) were shown to be monomeric by X-ray crystallography. In addition, the related β-diketiminato beryllium and calcium iodide complexes, [(MesNacnac)BeI] and [{(DippNacnac)-CaI(OEt2)} 2] were prepared and crystallographically characterized. The reductions of all metal(II) iodide complexes by using various reagents were attempted. In two cases these reactions led to the magnesium(I) dimers, [(MesNacnac)MgMg(MesNacnac)] and [(tBuNacnac)MgMg(tBuNacnac)]. The reduction of a 1:1 mixture of [(DippNacnac)MgI(OEt2)] and [(MesNacnac)MgI(OEt 2)] with potassium gave a low yield of the crystallo-graphically characterized complex [(DippNacnac)Mg(μ-H)(μ-I)Mg(MesNacnac)]. All attempts to form beryllium(I) or calcium(I) dimers by reductions of [(MesNacnac)BeI], [{(DippNacnac)CaI(OEt2)}2], or [{(tBuNacnac)CaI(thf)}2] have so far been unsuccessful. The further reactivity of the magnesium(I) complexes [(MesNacnac)MgMg(MesNacnac)] and [(tBuNacnac)MgMg(tBuNacnac)] towards a variety of Lewis bases and unsaturated organic substrates was explored. These studies led to the complexes[(MesNacnac) Mg(L)Mg(L)(MesNacnac)](L = THF or DMAP), [(MesNacnac)Mg-(μ-AdN 6Ad)Mg(MesNacnac)] (Ad = 1- adamantyl), [(tBuNacnac)Mg(μ-Ad-N 6Ad)Mg(tBuNacnac)], and [(MesNacnac)Mg(μ-tBu2N 2C2O2)Mg- (MesNacnac)] and revealed that, in general, the reactivity of the magnesium(I) dimers is inversely proportional to their steric bulk. The preparation and characterization of [(tBuNacnac)Mg(μ- H)2Mg(tBuNacnac)] has shown the compound to have different structural and physical properties to [(tBuNacnac)-MgMg(tBuNacnac)]. Treatment of the former with DMAP has given [(tBuNacnac)Mg(H)(DMAP)], the X-ray crystal structure of which disclosed it to be the first structurally authenticated terminal magnesium hydride complex. Although attempts to prepare [(MesNacnac)Mg(μ-H) 2Mg(MesNacnac)] were not successful, a neutron diffraction study of the corresponding magnesium(I) complex, [(MesNacnac)Mg-Mg(MesNacnac)] confirmed that the compound is devoid of hydride ligands.

Reactions of β-diketiminate-stabilized calcium amides with 9-borabicyclo[3.3.1]nonane (9-BBN)

The reaction of a β-diketiminate-stabilized calcium diphenylamide with the dialkylborane 9-BBN allows the synthesis of a β-diketiminate- stabilized calcium borohydride along with an amidoborane reaction coproduct via a likely σ-bond metathesis mechanism.