2016
DOI: 10.1002/anie.201606684
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Activation of Dihydrogen by Masked Doubly Bonded Aluminum Species

Koichi Nagata,
Takahiro Murosaki,
Tomohiro Agou
et al.

Abstract: Activation of dihydrogen by masked dialumenes (Al=Al doubly bonded species) is reported. Reactions of barrelene-type dialumanes, which have the reactivity as masked equivalents of 1,2-diaryldialumenes ArAl=AlAr, with H2 afforded dihydroalumanes ArAlH2 at room temperature (Ar: bulky aryl groups). These dihydroalumanes form hydrogen-bridged dimers [ArHAl(μ-H)]2 in the crystalline state, while a monomer-dimer equilibrium was suggested in solution. The 1,2-diaryldialumenes generated from the barrelene-type dialuma… Show more

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Cited by 45 publications
(28 citation statements)
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References 57 publications
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“…X-Ray diffraction analysis on single crystals of 3b revealed its molecular structure (Figure 1), [13] thereby showing ac entrosymmetric dimeric structure with the two aluminum atoms bridged by the hydrogen atoms.T he aluminum-bound hydrogen atoms (H1 and H2) were found in the Fourier map and refined isotropically.The bridging AlÀ Hbond lengths (1.72(2) and 1.68(2) )and the terminal AlÀ Hb ond length (1.60 (2) )a re comparable to those of the dihydroalumane dimer [Mes*HAl(m-H)] 2 (Al-H bridging 1.69(4) and 1.70(4) ,A l-H terminal 1.50(4) ,M es* = 2,4,6-(t-Bu) 3 C 6 H 2 ). [14] TheA l-Al distance (2.632(1) )i ss imilar to that of the reported dihydroalumane dimer [Mes*HAl(m-H)] 2 (2.652 (2) ).…”
Section: Dedicated To Professor Takayuki Kawashima On the Occasion Ofmentioning
confidence: 99%
“…X-Ray diffraction analysis on single crystals of 3b revealed its molecular structure (Figure 1), [13] thereby showing ac entrosymmetric dimeric structure with the two aluminum atoms bridged by the hydrogen atoms.T he aluminum-bound hydrogen atoms (H1 and H2) were found in the Fourier map and refined isotropically.The bridging AlÀ Hbond lengths (1.72(2) and 1.68(2) )and the terminal AlÀ Hb ond length (1.60 (2) )a re comparable to those of the dihydroalumane dimer [Mes*HAl(m-H)] 2 (Al-H bridging 1.69(4) and 1.70(4) ,A l-H terminal 1.50(4) ,M es* = 2,4,6-(t-Bu) 3 C 6 H 2 ). [14] TheA l-Al distance (2.632(1) )i ss imilar to that of the reported dihydroalumane dimer [Mes*HAl(m-H)] 2 (2.652 (2) ).…”
Section: Dedicated To Professor Takayuki Kawashima On the Occasion Ofmentioning
confidence: 99%
“…The bond angles around the aluminum atom (C1-Al1-N1 = 112.75(8), C1-Al1-N2 = 117.05 (8), and N1-Al1-N2 = 104.44(8) • ) imply some steric hindrance between these coordinating ligands. The Al-C bond length in 3 (2.031(2) Å) is elongated compared to those in 1 (1.970(2) Å) [16] and III (1.957(4) Å) [17], which may be associated with the increasing electron density at the aluminum center due to the coordination of the 1,4-dihydropyrid-1-yl and Py ligands. The lengths of the two Al-N bonds in 3 are distinctly different from each other; thus, the Al-N distance for the 1,4-dihydropyrid-1-yl group (Al1-N1 = 1.8568(19) Å) is much shorter than that for the coordinated Py (Al1-N2 = 2.0050(19) Å), each of which corresponds to the covalent and dative Al-N bonds [13].…”
Section: Structures Of Py→alh(14-dihydropyrid-1-yl)(eind) (3) and Ppmentioning
confidence: 88%
“…We have recently synthesized some new discrete aluminum hydride compounds by introducing bulky aryl groups [16,17]. As shown in Scheme 1a, the aryldihydroalumane dimer [dialumane (6)], (Eind)HAl(µ-H) 2 AlH(Eind) (1), incorporating the fused-ring bulky Eind groups (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), was obtained by the treatment of the lithium aryltrihydroaluminate dimer, [Li(OEt 2 )] 2 [(Eind)AlH 3 ] 2 (5), with chlorotrimethylsilane (Me 3 SiCl) [16].…”
Section: Introductionmentioning
confidence: 99%
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