Synthesis and Characterization of Gallium Silylamido Complexes

Carmalt, Claire J.; Mileham, John D.; White, Andrew J. P.; Williams, David J.; Steed, Jonathan W.

doi:10.1021/ic010507q

Cited by 35 publications

(38 citation statements)

References 31 publications

(38 reference statements)

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“…Carmalt et al have observed a similar Si-C bond cleavage in the reaction of GaCl 3 with (Me 3 Si) 3 N yielding among other things dimeric (MeGaCl 2 ) 2 . 9 Methyl-Exchange Reactions in Bis(trimethylsilyl)amino(dichloro)arsane (3). To gain further insight into GaCl 3 -assisted methyl/chlorine exchange reactions, we applied this reaction type to 3 and other arsenic species.…”

Section: Resultsmentioning

confidence: 99%

Lewis-Acid-Assisted Methyl Exchange Reactions In Silylated Aminodichloroarsanes

2008

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Lewis-acid-assisted methyl/chlorine, methyl/azide, and methyl/triflate exchange reactions between silicon and arsenic centers have been studied and applied to different silylated aminoarsane species leading to a number of new methylarsane compounds: bis(trimethylsilyl)amino(dichloro)arsane (3) was reacted with GaCl(3) yielding a bis(chlorodimethylsilyl)-tetramethyl-cyclo-disilazane (4) accompanied by the release of Me(2)AsCl, while trimethylsilyl(m-terphenyl)amino(dichloro)arsane (5) (m-terphenyl = 2,6-Mes(2)-C(6)H(3), Mes = 2,4,6-Me(3)C(6)H(2)) reacted with GaCl(3) to give dichloromethylsilyl(m-terphenyl)aminodimethylarsane (6). In the presence of trimethylsilylazide, trimethylsilyl(m-terphenyl)amino(dichloro)arsane displays a methyl/azide exchange triggered by the action of GaCl(3) yielding azidodimethylsilyl(m-terphenyl)amino(chloro)methylarsane (7). Moreover, methyl/triflate exchange reactions have been observed in the reaction of trimethylsilyl(m-terphenyl)amino(dichloro)arsane (i) with 1 equiv of AgOTf (OTf = triflate) yielding N-(trifluoromethylsulfonatodimethylsilyl)-N-(m-terphenyl)amino(methyl)chloroarsane (8) and (ii) with 2 equiv of AgOTf yielding N-(trifluoromethylsulfonatodimethylsilyl)-N-(m-terphenyl)trifluoromethylsulfonatomethylarsane (9). All new compounds (3-9) have been fully characterized by means of vibrational spectroscopy, X-ray, CHN analysis, MS, and NMR studies. A possible reaction mechanism is discussed starting from an initial chloride abstraction and the intermediate formation of a cationic iminoarsane species. In a second step, a methyl shift from the silicon to the arsenic center occurs.

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Section: Resultsmentioning

confidence: 99%

Lewis-Acid-Assisted Methyl Exchange Reactions In Silylated Aminodichloroarsanes

2008

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“…Selected bond lengths (Å) and angles (°): Ga1-C1 1.978(5), Ga1-N1 1.870(2), N1-Ga1-C1 117.71(1), N1-Ga1-N1′ 124.56(1). chloride complexes MeGaCl 2 (Carmalt et al, 2001;Lustig and Mitzel, 2004) and Me 2 GaCl (Lustig and Mitzel, 2004), the Ga-C bond lengths adopt much lower values of 1.921(3) and 1.933(7), respectively.…”

Section: Resultsmentioning

confidence: 98%

“…The formation of GaN films from single-source precursors depicts a more exploited field of application for gallium hydrides (see, e.g., Atwood et al, 1991a;McMurran et al, 1998;Carmalt et al, 2001;Luo et al, 2004). The most widely applied technique to generate GaN films is the dual-source chemical vapor deposition (CVD) of Me 3 Ga or Et 3 Ga with ammonia at high temperatures (Neumayer and Ekerdt, 1996).…”

Section: Introductionmentioning

confidence: 99%

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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“…29 This study examines and compares a selection of tungsten imido compounds, (3), (py = pyridine) and [W(N t Bu) 2 Cl(N{SiMe 3 } 2 )] (4) as potential (LP)CVD and (AA)CVD precursors. Although some of the compounds have been described previously, 5,30,31 their thermal properties have not been investigated and by tuning the ligands surrounding the tungsten centre we have successfully isolated some volatile precursors with ideal thermal properties for CVD.…”

Section: Introductionmentioning

confidence: 99%

Tungsten imido complexes as precursors to tungsten carbonitride thin films

et al. 2008

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Thin films of tungsten carbonitride have been formed on glass by low-pressure chemical vapour deposition (LP)CVD at 550 degrees C from four closely related precursors: [W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu)](2), [W(N(t)Bu)(2)Cl(2)(TMEDA)] (TMEDA = N,N,N',N'-tetramethylethylenediamine), [W(N(t)Bu)(2)Cl(2)(py)(2)] (py = pyridine) and [W(N(t)Bu)(2)Cl(N{SiMe(3)}(2))]. The grey mirror-like films were grown with a nitrogen or ammonia bleed gas. In all cases the chlorine content of the deposited films was less than 1 at% and the oxygen content of the films was lower for those grown using ammonia. Surprisingly, the use of ammonia did not significantly change the carbon content of the resulting films. Despite the coordination environment around the metal being essentially the same and the materials having a comparable volatility, some differences in film quality were observed. The films were uniform, adhesive, abrasion resistant, conformal and hard, being resistant to scratching with a steel scalpel. X-Ray powder diffraction patterns of all the films showed the formation of beta-WN(x)C(y). As a comparison the aerosol-assisted chemical vapour deposition (AA)CVD of [W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu)](2) was investigated and amorphous tungsten carbonitride films were deposited.

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Synthesis and Characterization of Gallium Silylamido Complexes

Cited by 35 publications

References 31 publications

Lewis-Acid-Assisted Methyl Exchange Reactions In Silylated Aminodichloroarsanes

Lewis-Acid-Assisted Methyl Exchange Reactions In Silylated Aminodichloroarsanes

Unusual reaction pathways of gallium(III) silylamide complexes

Tungsten imido complexes as precursors to tungsten carbonitride thin films

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