Crystal and molecular structure of an yttrium dicyclopentadienyl chloride complex with triethylaminalane [ν-(C5H5)2YCl · AlH3 · NEt3]2

Lobkovsky, Emil; Solveychik, Grigoriy L.; Булычев, Б. М.; Erofeev, A.B.; Gusev, A. I.; Kirillova, N. I.

doi:10.1016/s0022-328x(00)99103-4

Cited by 32 publications

(11 citation statements)

References 6 publications

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“…6 a, 6 b , and 7 b are the first examples of κ 2 σ‐gallane coordination to any transition metal. Indeed, σ‐gallane complexes in general have very little precedent, with those reported to date in the primary literature featuring κ 1 ‐ligation by either amine‐supported quinuclidine⋅GaH 3 or heterocyclic {HC(MeCDippN) 2 }GaH 2 5g. 11c…”

Section: Resultsmentioning

confidence: 99%

“…In the case of boranes, BH bond coordination (giving a σ‐complex) or activation (typically involving oxidative addition at a low‐valent transition‐metal centre) have been thoroughly investigated,5, 6 reflecting applications, for example, in various borylation reactions 7. 8 The corresponding chemistry of the heavier Group 13 element hydrides9 is much less well developed, with studies of σ‐complex formation and bond activation processes for AlH and GaH bonds being in their infancy 5f,g. 10–12 For example, to our knowledge, there are very few examples of oxidative activation of an AlH bond 12d.…”

Section: Introductionmentioning

confidence: 99%

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

Abdalla

Riddlestone

Turner

et al. 2014

Chemistry A European J

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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 κ(2) complexes of the type [M(CO)4 (κ(2)-H3 E⋅NHC)] with [M(CO)4 (COD)] (M=Cr, Mo), including the first κ(2) 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 κ(1) and κ(2) complexes were isolated, while [Cr(CO)4 (κ(2)-H2 Ga{(NDippCMe)2 CH})] is the only simple κ(2) 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)2 CH})]. Reaction of [Co2 (CO)8] with {HC(MeCDippN)2 }AlH2 generates [(OC)3 Co(μ-H)2 Al{(NdippCme)2 CH}][Co(CO)4] (12), which while retaining direct AlH interactions, features a hitherto unprecedented degree of bond activation in a σ-alane complex.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

Abdalla

Riddlestone

Turner

et al. 2014

Chemistry A European J

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“…14 The Cp 2 Y(μ‐H)Al structural motif was first observed in the 1980s 15. The groups of Bulychev and Soloveichik structurally characterized several complexes exhibiting Ln–H–Al moieties, as for example, in [(C 5 H 5 ) 2 YCl · AlH 3 · NEt 3 ] 2 ,16 [(C 5 H 5 ) 2 YAlH 4 · Do] 2 (Do = NEt 3 ,17 Et 2 O,17 thf18), and [(C 5 H 5 ) 2 Lu(μ‐H)AlH 3 · NEt 3 ],19 which were only soluble in benzene or thf. A more recent example, [(LScCl)(AlH 4 · thf 2 )] {L = (Ar)NC‐( t Bu)CHC( t Bu)N(Ar); Ar = 2,6‐ i Pr 2 C 6 H 3 }, was published by Piers et al20 In all of these complexes, a hydride bridges between a lanthanide metal and either an AlH 3 or an AlH 4 – moiety; however, a bridging hydride between a lanthanide and an alkyl or amide aluminum species has not been reported to date.…”

Section: Resultsmentioning

confidence: 99%

Rare‐Earth‐Metal‐Promoted Hydroalumination

Schädle

Anwander

2013

Eur J Inorg Chem

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The capability of bis(trimethylsilyl)amidoalane to act as a hydride transfer reagent in organolanthanide chemistry was investigated by probing its reactivity toward alkylyttrium complexes. Reaction with Cp*2YMe(thf) led to the isolation of the bimetallic complex Cp*2Y(μ‐H)2Al(Me)[N(SiMe3)2] (Cp* = 1,2,3,4,5‐pentamethylcyclopentadiene), whereas reaction with [Cp*YMe2]3 gave MeAl[N(SiMe3)2]2 as the only isolable hydride transfer product. The dimeric complex [Cp*Y{N(SiMe3)2}(μ‐H)]2 represents one possible product of the aforementioned reaction that could be structurally characterized. The use of [YMe3]n as the alkylyttrium source led to the isolation of Y[N(SiMe3)2]3, which displays competition between amide and hydride transfer. Finally, the performance of Cp*2Y(μ‐H)2Al(Me)[N(SiMe3)2] and [YMe3]n in the hydroalumination of 1‐octene was tested, and these compounds represent the first rare‐earth metal catalysts for this transformation.

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“…A number, such as [(Cp 2 YCl) 2 (H 3 AlÁNEt 3 )] 2 feature a neutral alane fragment linked to the metal centre not only via an Al-H-M unit, but also by a secondary interaction, in this case involving coordination of an yttrium-bound chloride ligand at aluminium. 20,21 Examples of simple, unsupported, charge neutral s-alane complexes such as L 3 Ni(HMe 2 AlÁquinuclidine) [L 3 = 1,5,9-cyclododecatriene or (CO) 3 ] and (Cp*Al) 3 Ni{HAl(Ph)Cp*} remain very rare. [20][21][22][23][24] In recent work targeting comparisons with more widely precedented families of E-H s-complexes (e.g.…”

mentioning

confidence: 99%

“…20,21 Examples of simple, unsupported, charge neutral s-alane complexes such as L 3 Ni(HMe 2 AlÁquinuclidine) [L 3 = 1,5,9-cyclododecatriene or (CO) 3 ] and (Cp*Al) 3 Ni{HAl(Ph)Cp*} remain very rare. [20][21][22][23][24] In recent work targeting comparisons with more widely precedented families of E-H s-complexes (e.g. E = H, B, Si), we have developed metathesis and photolytic carbonyl displacement routes to N-donor stabilized alane complexes of [CpMnL 2 ] and [W(CO) 3 L 2 ].…”

mentioning

confidence: 99%