Complications in metathesis reactions involving Grignard reagents: Effect of solvent on products obtained from the interaction of PhMgBr with GaCl3 or InBr3

Andrews, Philip C.; Junk, Peter Courtney; Nuzhnaya, Iryna; Spiccia, Leone; Vanderhoek, Nafty

doi:10.1016/j.jorganchem.2006.04.010

Cited by 8 publications

(1 citation statement)

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“…The cumulative results from this report on GaAs and GaN interfaces, in conjunction with our earlier study of GaP surfaces, indicate that the atop Ga atoms at the surfaces of binary III–V semiconductors are reactive toward alkylation reagents. The net process mirrors both the classic, homogeneous inorganic synthesis of organogallium compounds from GaCl 3 and alkyl Grignard reagents − and the more recently studied heterogeneous Si and Ge surface Grignard reaction chemistry. ,− Hence, the data shown here for atop Ga atoms at the GaAs(111)A, GaP(111)A, and GaN(0001) surface planes, in conjunction with relatively low reaction yields observed with the GaAs(111)B and GaP(111)B surface planes, support the contention that organic groups can be grafted specifically through surface Ga–C bonds.…”

Section: Discussionsupporting

confidence: 72%

Wet Chemical Functionalization of III–V Semiconductor Surfaces: Alkylation of Gallium Arsenide and Gallium Nitride by a Grignard Reaction Sequence

et al. 2012

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Crystalline gallium arsenide (GaAs) (111)A and gallium nitride (GaN) (0001) surfaces have been functionalized with alkyl groups via a sequential wet chemical chlorine activation, Grignard reaction process. For GaAs(111)A, etching in HCl in diethyl ether effected both oxide removal and surface-bound Cl. X-ray photoelectron (XP) spectra demonstrated selective surface chlorination after exposure to 2 M HCl in diethyl ether for freshly etched GaAs(111)A but not GaAs(111)B surfaces. GaN(0001) surfaces exposed to PCl(5) in chlorobenzene showed reproducible XP spectroscopic evidence for Cl-termination. The Cl-activated GaAs(111)A and GaN(0001) surfaces were both reactive toward alkyl Grignard reagents, with pronounced decreases in detectable Cl signal as measured by XP spectroscopy. Sessile contact angle measurements between water and GaAs(111)A interfaces after various levels of treatment showed that GaAs(111)A surfaces became significantly more hydrophobic following reaction with C(n)H(2n-1)MgCl (n = 1, 2, 4, 8, 14, 18). High-resolution As 3d XP spectra taken at various times during prolonged direct exposure to ambient lab air indicated that the resistance of GaAs(111)A to surface oxidation was greatly enhanced after reaction with Grignard reagents. GaAs(111)A surfaces terminated with C(18)H(37) groups were also used in Schottky heterojunctions with Hg. These heterojunctions exhibited better stability over repeated cycling than heterojunctions based on GaAs(111)A modified with C(18)H(37)S groups. Raman spectra were separately collected that suggested electronic passivation by surficial Ga-C bonds at GaAs(111)A. Specifically, GaAs(111)A surfaces reacted with alkyl Grignard reagents exhibited Raman signatures comparable to those of samples treated with 10% Na(2)S in tert-butanol. For GaN(0001), high-resolution C 1s spectra exhibited the characteristic low binding energy shoulder demonstrative of surface Ga-C bonds following reaction with CH(3)MgCl. In addition, 4-fluorophenyl groups were attached and detected after reaction with C(6)H(4)FMgBr, further confirming the susceptibility of Cl-terminated GaN(0001) to surface alkylation. However, the measured hydrophobicities of alkyl-terminated GaAs(111)A and GaN(0001) were markedly distinct, indicating differences in the resultant surface layers. The results presented here, in conjunction with previous studies on GaP, show that atop Ga atoms at these crystallographically related surfaces can be deliberately functionalized and protected through Ga-C surface bonds that do not involve thiol/sulfide chemistry or gas-phase pretreatments.

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Section: Discussionsupporting

confidence: 72%

Wet Chemical Functionalization of III–V Semiconductor Surfaces: Alkylation of Gallium Arsenide and Gallium Nitride by a Grignard Reaction Sequence

et al. 2012

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Indium: Organometallic Chemistry

Banger

2015

Encyclopedia of Inorganic and Bioinorganic Chemistry

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An update for select advances in the chemistry of organoindium compounds containing at least one In–C bond is reported. In particular, the various synthesis protocols to these are discussed, as well as characterization of homoleptic and heteroleptic organoindium derivatives; organoindium (0), (I), and ( II ) compounds; and anionic compounds is also reported. An examination of mixed metal complexes is also reported for both low valent systems as well as for In( III ) oxidation state. Furthermore, the use of organoindium compounds for thin film, nanotechnology organic synthesis, and catalysis is discussed.

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Grignard metathesis

Drees¹

2020

Catalysis From a to Z

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Complications in metathesis reactions involving Grignard reagents: Effect of solvent on products obtained from the interaction of PhMgBr with GaCl3 or InBr3

Cited by 8 publications

References 17 publications

Wet Chemical Functionalization of III–V Semiconductor Surfaces: Alkylation of Gallium Arsenide and Gallium Nitride by a Grignard Reaction Sequence

Wet Chemical Functionalization of III–V Semiconductor Surfaces: Alkylation of Gallium Arsenide and Gallium Nitride by a Grignard Reaction Sequence

Indium: Organometallic Chemistry

Grignard metathesis

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