Coordination and Activation of AlH and GaH Bonds. Issue 52 (30th October 2014)

• Record Type: Journal Article
• Authors: Abdalla, Joseph A. B.; Riddlestone, Ian M.; Turner, Joshua; Kaufman, Paul A.; Tirfoin, Remi; Phillips, Nicholas; Aldridge, Simon
• Is Part Of: Chemistry. Volume 20:Issue 52(2014)
• Page Start: 17624
• Page End: 17634
• Publication Date: 2014-10-30
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201405018
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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] (<bold>12</bold>), which while retaining direct AlH interactions, features a hitherto unprecedented degree of bond activation in a σ‐alane complex.</p> </abstract>