Coordination and Activation of AlH and GaH Bonds

The modes of interaction of donor‐stabilized Group 13 hydrides (E=Al, Ga) were investigated towards 14‐ and 16‐electron transition‐metal fragments. More electron‐rich N‐heterocyclic carbene‐stabilized alanes/gallanes of the type NHC⋅EH3 (E=Al or Ga) exclusively generate κ2 complexes of the type [M(C...

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Published in:Chemistry : a European journal 2014-12, Vol.20 (52), p.17624-17634
Main Authors: Abdalla, Joseph A. B., Riddlestone, Ian M., Turner, Joshua, Kaufman, Paul A., Tirfoin, Remi, Phillips, Nicholas, Aldridge, Simon
Format: Article
Language:English
Subjects:
Activation
alanes
Aluminium
Aluminum
Carbenes
Carbonyls
Dehydrogenation
Fragments
gallanes
Group 6 elements
Hydrides
σ-complexes
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Summary:The modes of interaction of donor‐stabilized Group 13 hydrides (E=Al, Ga) were investigated towards 14‐ and 16‐electron transition‐metal fragments. More electron‐rich N‐heterocyclic carbene‐stabilized alanes/gallanes of the type NHC⋅EH3 (E=Al or Ga) exclusively generate κ2 complexes of the type [M(CO)4(κ2‐H3E⋅NHC)] with [M(CO)4(COD)] (M=Cr, Mo), including the first κ2 σ‐gallane complexes. β‐Diketiminato (′nacnac′)‐stabilized systems, {HC(MeCNDipp)2}EH2, show more diverse reactivity towards Group 6 carbonyl reagents. For {HC(MeCNDipp)2}AlH2, both κ1 and κ2 complexes were isolated, while [Cr(CO)4(κ2‐H2Ga{(NDippCMe)2CH})] is the only simple κ2 adduct of the nacnac‐stabilized gallane which can be trapped, albeit as a co‐crystallite with the (dehydrogenated) gallylene system [Cr(CO)5(Ga{(NDippCMe)2CH})]. Reaction of [Co2(CO)8] with {HC(MeCDippN)2}AlH2 generates [(OC)3Co(μ‐H)2Al{(NdippCme)2CH}][Co(CO)4] (12), which while retaining direct AlH interactions, features a hitherto unprecedented degree of bond activation in a σ‐alane complex. The modes of interaction of aluminium and gallium hydrides towards 14‐ and 16‐electron transition‐metal fragments were investigated. More electron‐rich N‐heterocyclic carbene compounds (NHC⋅EH3; E=Al or Ga) uniformly generate κ2 σ‐complexes. By contrast, β‐diketiminato (nacnac)‐stabilized systems, {HC(MeCDippN)2}EH2, show more diversity, including examples of unprecedented EH bond activation.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201405018