Structure of bis-μ-[(trimethylsilylmethanolato-O)-bis(trimethylsilylmethyl)gallium] and bis-μ-[(trimethylsilylmethanolato-O)-bis(trimethylsilylmethyl)indium]

Dembowski, U.; Pape, Tania; Herbst‐Irmer, Regine; Pohl, Ehmke; Roesky, H. W.; Sheldrick, George M.

doi:10.1107/s0108270192013337

Cited by 8 publications

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“…In the compounds where there is hydrogen bonding between cations and alkoxide oxygen atoms, the corresponding In−O distances are lengthened slightly by the interaction. The cluster In 5 (μ 5 -O)(μ 3 -O- i -Pr) 4 (μ 2 -O- i -Pr) 4 (O- i -Pr) 5 is the only other structurally characterized indium complex with terminal In−OR bonds, and in it, the distances are 1.957(15)−1.988(16) Å, which are close to the short end of the range we observe. , The In−O bridge bond distances in 1 [2.129(5) and 2.134(5) Å] are similar to the distances reported for the In 2 (μ-OR) 2 cores in alkylindium alkoxide dimers: [ t -Bu 2 In(μ-OMe)] 2 [average 2.153(2) Å], [ t -Bu 2 In(μ-OEt)] 2 [average 2.156(5) Å], [Ph 2 In(μ-OSiMe 3 )] 2 [average 2.154(8) Å], and [(Me 3 SiCH 2 ) 2 In(μ-OSiMe 3 )] 2 [average 2.163(7) Å] . The In−O bridge distances in [In(μ-OC 2 H 5 )(SC 5 H 4 N) 2 ] 2 , a dimer with octahedral In atoms, average 2.132(3) Å .…”

Section: Resultssupporting

confidence: 79%

“…17,18 The In-O bridge bond distances in 1 [2.129(5) and 2.134(5) Å] are similar to the distances reported for the In 2 (µ-OR) 2 cores in alkylindium alkoxide dimers: [t-Bu 2 -In(µ-OMe)] 2 [average 2.153(2) Å], 19 [t-Bu 2 In(µ-OEt)] 2 [average 2.156( 5) Å], 20 [Ph 2 In(µ-OSiMe 3 )] 2 [average 2.154(8) Å], 21 and [(Me 3 SiCH 2 ) 2 In(µ-OSiMe 3 )] 2 [average 2.163(7) Å]. 22 The In-O bridge distances in [In(µ-OC 2 H 5 )(SC 5 H 4 N) 2 ] 2 , a dimer with octahedral In atoms, average 2.132(3) Å. 23 Interestingly, the distances in the indium(I) dimer [In(µ-O-2,4,6-(CF 3 ) 3 C 6 H 2 )] 2 (average 2.320 Å), 11 which has an empty p orbital on each In atom available for π interaction, are significantly longer than those in the indium(III) compounds, the opposite of what might have been expected.…”

Section: Resultsmentioning

confidence: 99%

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Indium Fluoroalkoxide Compounds

1999

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Reactions of indium amide complexes with fluorinated alcohols give indium fluoroalkoxide complexes. In[N-t-Bu(SiMe(3))](3) reacts with 3 equiv of (CF(3))Me(2)COH to give the homoleptic alkoxide dimer [In{&mgr;-OCMe(2)(CF(3))}{OCMe(2)(CF(3))}(2)](2), but reactions involving the more acidic alcohols (CF(3))(2)MeCOH and (CF(3))(2)CHOH yield products containing t-BuNH(2), which is derived from the amide ligands. Thus, In[N-t-Bu(SiMe(3))](3) reacts with (CF(3))(2)MeCOH to give In[OCMe(CF(3))(2)](3)(H(2)N-t-Bu) and with (CF(3))(2)CHOH to yield In[OCH(CF(3))(2)](3)(H(2)N-t-Bu)(3) and [H(3)N-t-Bu][In{OCH(CF(3))(2)}(4)(H(2)N-t-Bu)]. Reactions of (CF(3))(2)MeCOH and (CF(3))(2)CHOH with In(tmp)(3) (tmp = the anion derived from 2,2,6,6-tetramethylpiperidine) and In(NEt(2))(3) are less complicated. In(tmp)(3) reacts with 3 equiv of (CF(3))(2)CHOH to give In[OCH(CF(3))(2)](3)(Htmp) and with 4 equiv of (CF(3))(2)CHOH or (CF(3))(2)MeCOH to yield the salt compounds [H(2)tmp][In{OCR(CF(3))(2)}(4)] (R = H, Me). Trigonal bipyramidal [H(2)NEt(2)][In{OCH(CF(3))(2)}(4)(HNEt(2))] and octahedral mer-In[OCMe(CF(3))(2)](3)(py)(3) are isolated from reactions involving In(NEt(2))(3). Crystal structure determinations of [In{&mgr;-OCMe(2)(CF(3))}{OCMe(2)(CF(3))}(2)](2), [H(3)N-t-Bu][In{OCH(CF(3))(2)}(4)(H(2)N-t-Bu)].EtOEt, In[OCH(CF(3))(2)](3)(Htmp), [H(2)tmp][In{OCMe(CF(3))(2)}(4)], In[OCMe(CF(3))(2)](3)(py)(3), and [H(2)NEt(2)][In{OCH(CF(3))(2)}(4)(HNEt(2))] were carried out.

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Section: Resultssupporting

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Indium Fluoroalkoxide Compounds

1999

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“…34 The In-OR terminal and In-OR bridge distances in the new complexes are not unusual. 25,26,32,[43][44][45][46][47] The In-N distance in 9 is about 0.1 Å shorter than the In-N distances in 7 and 8 and is shorter than most previously observed In-N(amine) distances [2.200(19)-2.408( 7) Å]. 28,31,32,34,[48][49][50][51][52][53][54][55] It is tempting to ascribe the short In-N distance in 9 to the enhanced donor ability of (9), and (t-BuO)2In(µ-O-t-Bu)2In(t-Bu2-β-diketonate)2 ( 10 flow controllers.…”

Section: Methodsmentioning

confidence: 99%

General Synthesis of Homoleptic Indium Alkoxide Complexes and the Chemical Vapor Deposition of Indium Oxide Films

and

Hoffman

2000

J. Am. Chem. Soc.

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A general synthetic route to homoleptic indium alkoxide complexes was developed, and one of the new compounds was used as a precursor to transparent, conductive indium oxide films. The amide complex In[N-t-Bu(SiMe 3 )] 3 reacted with t-BuOH, EtMe 2 COH, Et 2 MeCOH and i-PrMe 2 COH to yield the dimers [In-(µ-OR)(OR) 2 ] 2 (R ) t-Bu, CMe 2 Et, CMeEt 2 , and CMe 2 i-Pr) in high yield. Similar reactions of In[N-t-Bu-(SiMe 3 )] 3 with the less bulky alcohols i-PrOH and Et 2 HCOH yielded, respectively, insoluble [In(O-i-Pr) 3 ] n and the tetramer In[(µ-OCHEt 2 ) 2 In(OCHEt 2 ) 2 ] 3 , which has a six-coordinate central indium atom surrounded by three four-coordinate indium atoms. The compounds [In(O-i-Pr) 3 ] n and In[(µ-OCHEt 2 ) 2 In(OCHEt 2 ) 2 ] 3 were also prepared by reacting [In(µ-O-t-Bu)(O-t-Bu) 2 ] 2 with an excess of the respective alcohols. Attempts to prepare the previously reported oxo cluster In 5 (µ 5 -O)(µ 3 -O-i-Pr) 4 (µ 2 -O-i-Pr) 4 (O-i-Pr) 5 by thermally decomposing [In(O-i-Pr) 3 ] n failed. The reaction between In[N-t-Bu(SiMe 3 )] 3 and 2,6-diisopropylphenol afforded the bis tertbutylamine adduct In(O-2,6-i-Pr 2 C 6 H 3 ) 3 (H 2 N-t-Bu) 2 . The evidence suggests that the tert-butylamine ligands in In(O-2,6-i-Pr 2 C 6 H 3 ) 3 (H 2 N-t-Bu) 2 resulted from a secondary reaction between HN-t-Bu(SiMe 3 ) and 2,6diisopropylphenol. The powerful donor p-(dimethylamino)pyridine (p-Me 2 Npy) reacted with [In(µ-O-t-Bu)-(O-t-Bu) 2 ] 2 to yield 5-coordinate In(O-t-Bu) 3 (p-Me 2 Npy) 2 and with the more sterically encumbered complex [In(µ-OCMeEt 2 )(OCMeEt 2 ) 2 ] 2 to yield four-coordinate In(OCMeEt 2 ) 3 (p-Me 2 Npy). In addition, [Inwhich has four-and six-coordinate indium centers and virtual C 2 symmetry. X-ray crystallographic studies were carried out for [In(OCMeEt 2 ) 3 (p-Me 2 Npy), and (t-BuO) 2 In(µ-O-t-Bu) 2 In(t-Bu 2 -β-diketonate) 2 . The t-amoxide complex [In(OCMe 2 Et) 3 ] 2 and oxygen were used as precursors to deposit transparent, highly conductive indium oxide films on silicon, glass, and quartz substrates at substrate temperatures of 300-500 °C in a low-pressure chemical vapor deposition process. A backscattering spectrum indicated the film deposited at 500 °C was stoichiometric In 2 O 3 (O/In ) 1.46 ( 0.07). The films were transparent in the visible region (>75%) and had resistivities as low as 9.1 × 10 -4 Ω cm. X-ray diffraction studies indicated the films deposited on glass were cubic and highly (100) oriented.

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“…Die Ga±O-Bindungsla È ngen sind mit 193,3(2) und 196,2(3) pm nicht ungewo È hnlich. In der Verbindung [(Me 3 SiCH 2 ) 2 GaOCH 2 SiMe 3 ] 2 betra È gt die Ga±O-Bindungsla È nge beispielsweise 196,7(4) pm [10].…”

Section: Introductionunclassified