Synthesis and molecular structure of an unusual –Ga–Ga–Ga– linked organometallic

Li, Xiao-Wang; Wei, Pingrong; Beck, Brent C.; Xie, Yaoming; Schaefer, Henry F.; Su, Jianzhong; Robinson, Gregory H.

doi:10.1039/a909451b

Cited by 21 publications

(13 citation statements)

References 15 publications

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“…Isobutene elimination was observed as well. A more unusual hydride formation has been found upon the reaction of [(2,4,6-i Pr 3 C 6 H 2 ) 2 C 6 H 3 ]GaCl 2 with P(SiMe 3 ) 3 , yielding the Ga-Ga-Ga chain complex [(2,4,6-i Pr 3 C 6 H 2 ) 2 C 6 H 3 ] Ga{H 2 PGa(H)PH 2 }Ga[(2,4,6-i Pr 3 C 6 H 2 ) 2 C 6 H 3 ] (Chart 2D) (Li et al, 2000). Li et al suggest that the hydride could arise from a stripped m-terphenyl ligand or even from the solvent.…”

Section: Resultsmentioning

confidence: 97%

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Unusual reaction pathways of gallium(III) silylamide complexes

Koenig

Gerstberger

Schaedle

et al. 2013

Main Group Metal Chemistry

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The synthesis of homoleptic gallium(III) bis(dimethylsilyl)amide Ga[N(SiHMe 2 ) 2 ] 3 was attempted via different pathways. A transsilylamination protocol using Ga[N(SiMe 3 ) 2 ] 3 and HN(SiHMe 2 ) 2 was unsuccessfully applied. An unexpected side product, MeGa[N(SiMe 3 ) SiMe 2 N(SiMe 3 ) 2 ] 2 , could be obtained from the synthesis of homoleptic gallium(III) bis(trimethylsilyl)amide via GaCl 3 and LiN(SiMe 3 ) 2 . Alkane elimination from Me 3 Ga or Et 3 Ga and HN(SiHMe 2 ) 2 did not lead to the isolation of Ga[N(SiHMe 2 ) 2 ] 3 either. When a salt metathesis route was conducted, reacting GaCl 3 with LiN(SiHMe 2 ) 2 , the silylamido-bridged dimeric hydride complex {H 2 Ga[μ-N(SiHMe 2 ) 2 ]} 2 was obtained. Its further reaction with N,N,N′,N′-tetramethylethylendiamine (tmeda) gave the dinuclear, tmeda-bridged {[H 2 GaN(SiHMe 2 ) 2 ] 2 (μ-tmeda)}.

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Section: Resultsmentioning

confidence: 97%

“…(C) Mes* 2 GaH (Wehmschulte et al, 1994). (D) [(2,4,6-i Pr 3 C 6 H 2 ) 2 C 6 H 3 ]Ga{H 2 PGa(H)PH 2 }Ga[(2,4,6-i Pr 3 C 6 H 2 ) 2 C 6 H 3 ] (Li et al, 2000). solution, crystals of {[(SiHMe 2 ) 2 N] 2 Al[μ-N(H)(SiHMe 2 )]} 2 (3a) were obtained and characterized by X-ray crystallography (Scheme 2, Figure 4).…”

Section: Resultsmentioning

confidence: 99%

Unusual reaction pathways of gallium(III) silylamide complexes

Koenig

Gerstberger

Schaedle

et al. 2013

Main Group Metal Chemistry

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“…[20][21][22][23][24] The computed 1 H NMR spectrum of a model of 1, [(C 10 H 8 )(CpZr) 2 (m-H)(m-Cl)(m-GaR)] (1 a; R = 2,6-Me 2 C 6 H 3 ), at the GIAO-PW91PW91/ LANL2DZ/-/PW91/LANL2DZ level showed that the computed hydride d value of À5.00 ppm is comparable to the experimental value observed for 1. [27][28][29][30] In an effort to better elucidate the nature of the hydride, we performed density functional theory (DFT) computations on 1 a, in which the meta terphenyl ligand of 1 has been replaced with a 2,6-dimethylphenyl ligand. This phenomenon-in which a hydride was clearly observed in the 1 H NMR spectrum as a singlet at d = À9.3 ppm but was undetected by X-ray or IR analyses-was reported for [(Cp 2 Zr) 2 (m-C 10 H 7 )(m-H)].…”

Section: ]-[Cp 2 Zr{ga[n(aryl)c(h)] 2 } 2 ]mentioning

confidence: 99%

A Trimetallic Fulvalene‐Bridged Dizirconocene–Gallium Complex

et al. 2007

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Eine Galliumbrücke: Die Röntgenstrukturanalyse von 1 (siehe Bild; Ga rosa, Zr blau, Cl grün, C gelb) ergab ein neuartiges Metall‐Metall‐Bindungsmotiv zwischen Gallium‐ und Zirconiumatomen: ein an zwei Zirconiumatome gebundenes Galliumatom. Spektroskopische und Computerdaten sprechen für das Vorliegen eines verbrückenden Zr‐H‐Zr‐Hydrids in 1, das bei der Einkristallstrukturanalyse nicht entdeckt wurde.

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“…2 ). 8 One potential route to low oxidation state group 13 metal hydride complexes is via the reactions of metal trihydride complexes with reductants or radical hydrogen abstraction reagents. Of the latter, 2,2 0 ,6,6 0 -tetramethylpiperidinyl oxide (TEMPO) offered promise as it has been shown to homolytically cleave other p-block metal-hydrogen bonds (e.g.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterisation of tetramethylpiperidinyloxide (TEMPO) complexes of group 13 metal hydrides

Jones

Rose

2007

New J. Chem.

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Attempts have been made to prepare low oxidation state group 13 hydride complexes by reacting the metal trihydride-Lewis base adducts, [MH 3 (quin)] (quin = quinuclidine, M = Al, Ga or In), with reducing or hydrogen abstraction reagents. The 1 : 1 reactions with 2,2 0 ,6,6 0tetramethylpiperidinyl oxide (TEMPO) yield the first structurally characterised nitroxide-group 13 hydride complexes, [MH 2 (quin)(TEMPO)] (M = Al or Ga). The 2 : 1 reaction with [AlH 3 (quin)] affords [AlH(quin)(TEMPO) 2 ] which has also been structurally authenticated. The mechanisms of these reactions are discussed.

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Synthesis and molecular structure of an unusual –Ga–Ga–Ga– linked organometallic

Cited by 21 publications

References 15 publications

Unusual reaction pathways of gallium(III) silylamide complexes

Unusual reaction pathways of gallium(III) silylamide complexes

A Trimetallic Fulvalene‐Bridged Dizirconocene–Gallium Complex

Synthesis and characterisation of tetramethylpiperidinyloxide (TEMPO) complexes of group 13 metal hydrides

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