Molecular Alumo- and Gallosilicate Hydrides Functionalized with Terminal M(NR2)3 and Bridging M(NR2)2 (M = Ti, Zr, Hf; R = Me, Et) Moieties.

A general synthetic strategy for the systematic synthesis of group 4 MIV heterometallic complexes LMIII(H)(µ-O)Si(µ-O)(OtBu)2}nMIV(NR2)4-n (L = {[HC{C(Me)N(2,6-iPr2C6H3)}2; MIII = Al or Ga; n = 1 or 2; MIV = Ti, Zr, Hf; R = Me, Et), based on alumo- or gallosilicate hydride ligands bearing a Si-OH moiety, is presented. The challenging isolation of these metalloligands involved two strategies. On the one hand, the acid-base reaction of LAlH2 with (HO)2Si(OtBu)2 yielded LAlH(µ-O)Si(OH)(OtBu)2 (1), while on the other hand, the oxidative addition of (HO)2Si(OtBu)2 to LGa produced the gallium analog (2). These metalloligands successfully stabilized two hydrogen atoms with different acid-base properties (MIII-H and SiO-H) in the same molecule. Reactivity studies between 1 and 2 and group 4 amides MIV(NR2)4 (MIV = Ti, Zr, Hf; R = Me, Et) and tuning the reactions conditions and stoichiometry led to isolation and structural characterization of heterometallic complexes 3-11 with a 1:1 or 2:1 metalloligand/MIV ratio. Notably, some of these molecular heterometallic silicate complexes stabilize for the first time terminal (O3Si-O-)MIV(NR2)3 moieties known from single-site silica-grafted species. Furthermore, the aluminum-containing heterometallic complexes possess Al-H vibrational energies similar to those reported for modified alumina surfaces, which makes them potentially suitable models for the proposed MIV species grafted onto silica/alumina surfaces with hydride and dihydride architectures.

Synthesis of substituted ß-diketiminate gallium hydrides via oxidative addition of H-O bonds.

Oxidative addition of LGa into the OH bonds from HCCCH2OH, Ph2Si(OH)2, (nBuO)2P(O)(OH) and 4-MeC6H4S(O)2(OH) results in the formation of four compounds of the general formula LGa(H)(O-X). The correlation of the Ga-O bond length and the strength of the Ga-H bond depending on the acidity of the OH group in the starting materials has been demonstrated. The molecular structures of all four compounds have been determined using single crystal X-ray diffraction experiments. DFT calculations were performed on the reacting complex of LGa with propargyl alcohol and show an OHGa hydrogen bond as the first interaction between the reagents. This reacting complex changes into a D-A complex where the oxygen atom of the propargyl alcohol coordinates to the gallium atom and in a concerted reaction the oxidative addition product is formed.