Synthesis and purification of trimethylgallium for MOCVD: molecular structure of (KF)4�4(Me3Ga)

Abstract

Trimethylgallium was obtained from a 3:1 molar mixture of Me 2 AlCl (1) and GaCl 3 (2) only in the presence of NaCl. The mechanism of the reaction was traced. It is postulated that the gallium-aluminium dimers Cl n Me 2Àn AlCl 2 GaCl m Me 2Àm (m and n = 0, 1 or 2), formed in consecutive alkylation steps, do not participate in further alkyl-chlorine exchange. NaCl splits the dimers that form the precipitate of Na[Me-AlCl 3 ] (3), thus liberating Me n GaCl 3Àn which, on further alkylation by Me 2 AlCl, finally yields Me 3 Ga. For an MOCVD application, it is purified through a complex with KF, which under vacuum decomposes at 180-300°C, to yield a product contaminated by less than 1 ppm of the total impurities. The X-ray study of the complex reveals a tetrameric, highly symmetrical heterocubane of formula (KF) 4 Á4(Me 3 Ga).

Heteroselective Polymerization of rac-Lactide in the Presence of Dialkylgallium Alkoxides: The Effect of Lewis Base on Polymerization Stereoselectivity

“…( S )-Methyl lactate was purchased from Aldrich, dried over molecular sieves, and distilled under nitrogen. Me 3 Ga and [Me 2 Ga(μ-OCH 2 CH 2 OMe)] 2 ( 2 ) were synthesized according to the literature. 1 H NMR spectra were recorded on a Varian Mercury 400 MHz or a Varian Unity 200 MHz spectrometer, with shifts given in ppm referenced to the deuterated solvent shift.…”

Heteroselective Polymerization of rac-Lactide in the Presence of Dialkylgallium Alkoxides: The Effect of Lewis Base on Polymerization Stereoselectivity

“…( S )-Methyl lactate was purchased from Aldrich, dried over molecular sieves, and distilled under nitrogen. Me 3 Ga and [Me 2 Ga(μ-OCH 2 CH 2 OMe)] 2 ( 2 ) were synthesized according to the literature. 1 H NMR spectra were recorded on a Varian Mercury 400 MHz or a Varian Unity 200 MHz spectrometer, with shifts given in ppm referenced to the deuterated solvent shift.…”

Development of Reuse Process Through Recovery and Refinement of Precursor for LED

“…트리메틸갈륨(Ga(CH 3 ) 3 , TMGa)은 1933년도에 처 음 논문으로 발표되었으며, 1,2) 그 후 Ga(CH 3 ) 3 을 만 드는 수많은 방법들이 논문으로 출간되었다. [2][3][4] 그 방 법 중 주로 사용하는 방법은 삼중염화 갈륨과 이중메 틸 아연을 반응시키는 방법이며, 참고문헌에 자세히 소개되어있다. 2) 트리메틸갈륨은 organometallic vapor phase epitaxy(MOVPE) 장치로 고품질의 GaAs 및 GaN 화합물 계열을 성장시킬 때 원료로 널리 사용되 고 있으며, [5][6][7][8] 일반적인 유기금속화합물을 만들 때에 도 사용된다.…”

Untitled

“…31 A more complex preparation for very pure Me 3 Ga involved the KF adduct (KF) 4 (Me 3 Ga) 4 for which an X-ray crystallographic study revealed a highly symmetrical heterocubane structure. 32 Intramolecular base stabilisation of the metal center of precursor compounds makes them much less reactive towards moisture and air, examples of this were cyclopentadienylaluminium and gallium dihydrides employing an amine-substituted cyclopentadienyl ring, e.g. [(R 2 NCH 2 CH 2 )C 5 H 4 ]MH 2 (R = Me or Pr i , M = Al or Ga) 33 and [Me 2 N(CH 2 ) 3 ]GaMe 2 .…”

Heteroselective Polymerization of rac-Lactide in the Presence of Dialkylgallium Alkoxides: The Effect of Lewis Base on Polymerization Stereoselectivity

“…( S )-Methyl lactate was purchased from Aldrich, dried over molecular sieves, and distilled under nitrogen. Me 3 Ga and [Me 2 Ga(μ-OCH 2 CH 2 OMe)] 2 ( 2 ) were synthesized according to the literature. 1 H NMR spectra were recorded on a Varian Mercury 400 MHz or a Varian Unity 200 MHz spectrometer, with shifts given in ppm referenced to the deuterated solvent shift.…”

Development of Reuse Process Through Recovery and Refinement of Precursor for LED

“…트리메틸갈륨(Ga(CH 3 ) 3 , TMGa)은 1933년도에 처 음 논문으로 발표되었으며, 1,2) 그 후 Ga(CH 3 ) 3 을 만 드는 수많은 방법들이 논문으로 출간되었다. [2][3][4] 그 방 법 중 주로 사용하는 방법은 삼중염화 갈륨과 이중메 틸 아연을 반응시키는 방법이며, 참고문헌에 자세히 소개되어있다. 2) 트리메틸갈륨은 organometallic vapor phase epitaxy(MOVPE) 장치로 고품질의 GaAs 및 GaN 화합물 계열을 성장시킬 때 원료로 널리 사용되 고 있으며, [5][6][7][8] 일반적인 유기금속화합물을 만들 때에 도 사용된다.…”

Untitled

“…31 A more complex preparation for very pure Me 3 Ga involved the KF adduct (KF) 4 (Me 3 Ga) 4 for which an X-ray crystallographic study revealed a highly symmetrical heterocubane structure. 32 Intramolecular base stabilisation of the metal center of precursor compounds makes them much less reactive towards moisture and air, examples of this were cyclopentadienylaluminium and gallium dihydrides employing an amine-substituted cyclopentadienyl ring, e.g. [(R 2 NCH 2 CH 2 )C 5 H 4 ]MH 2 (R = Me or Pr i , M = Al or Ga) 33 and [Me 2 N(CH 2 ) 3 ]GaMe 2 .…”

Heteroselective Polymerization of rac-Lactide in the Presence of Dialkylgallium Alkoxides: The Effect of Lewis Base on Polymerization Stereoselectivity

“…( S )-Methyl lactate was purchased from Aldrich, dried over molecular sieves, and distilled under nitrogen. Me 3 Ga and [Me 2 Ga(μ-OCH 2 CH 2 OMe)] 2 ( 2 ) were synthesized according to the literature. 1 H NMR spectra were recorded on a Varian Mercury 400 MHz or a Varian Unity 200 MHz spectrometer, with shifts given in ppm referenced to the deuterated solvent shift.…”

Development of Reuse Process Through Recovery and Refinement of Precursor for LED

“…트리메틸갈륨(Ga(CH 3 ) 3 , TMGa)은 1933년도에 처 음 논문으로 발표되었으며, 1,2) 그 후 Ga(CH 3 ) 3 을 만 드는 수많은 방법들이 논문으로 출간되었다. [2][3][4] 그 방 법 중 주로 사용하는 방법은 삼중염화 갈륨과 이중메 틸 아연을 반응시키는 방법이며, 참고문헌에 자세히 소개되어있다. 2) 트리메틸갈륨은 organometallic vapor phase epitaxy(MOVPE) 장치로 고품질의 GaAs 및 GaN 화합물 계열을 성장시킬 때 원료로 널리 사용되 고 있으며, [5][6][7][8] 일반적인 유기금속화합물을 만들 때에 도 사용된다.…”

Untitled

“…31 A more complex preparation for very pure Me 3 Ga involved the KF adduct (KF) 4 (Me 3 Ga) 4 for which an X-ray crystallographic study revealed a highly symmetrical heterocubane structure. 32 Intramolecular base stabilisation of the metal center of precursor compounds makes them much less reactive towards moisture and air, examples of this were cyclopentadienylaluminium and gallium dihydrides employing an amine-substituted cyclopentadienyl ring, e.g. [(R 2 NCH 2 CH 2 )C 5 H 4 ]MH 2 (R = Me or Pr i , M = Al or Ga) 33 and [Me 2 N(CH 2 ) 3 ]GaMe 2 .…”