Synthetic and Structural Studies of Donor-Functionalized Alkoxy Derivatives of Gallium

Abstract

The synthesis of a range of alkyl/chloro-gallium alkoxide and amido/alkoxide compounds was achieved via a series of protonolysis and alcoholysis steps. The initial reaction involved the synthesis of [Me(Cl)Ga{N(SiMe(3))(2)}](2) (1) via methyl group transfer from the reaction of GaCl(3) with two equivalents of LiN(SiMe(3))(2). Reaction of 1 with varying amounts of ROH resulted in the formation of [Me(Cl)Ga(OR)](2) (2, R = CH(2)CH(2)OMe; 3, CH(CH(3))CH(2)NMe(2)), [Me(Cl)Ga{N(SiMe(3))(2)}(μ(2)-OR)Ga(Cl)Me] (4, R = CH(2)CH(2)NMe(2)), or [MeGa(OR)(2)] (5, R = CH(CH(3))CH(2)NMe(2)). Compound 4 represents an intermediate in the formation of dimeric complexes, of the type [Me(Cl)Ga(OR)](2), when formed from compound [Me(Cl)Ga{N(SiMe(3))(2)}](2). A methylgallium amido/alkoxide complex [MeGa{N(SiMe(3))(2)}(OCH(2)CH(2)OMe)](2) (6) was isolated when 2 was further reacted with LiN(SiMe(3))(2). In addition, reaction of 2 with HO(t)Bu resulted in a simple alcohol/alkoxide exchange and formation of [Me(Cl)Ga(O(t)Bu)](2) (7). In contrast to the formation of 1, the in situ reaction of GaCl(3) with one equivalent of LiN(SiMe(3))(2) yielded [Cl(2)Ga{N(SiMe(3))(2)}](2) in low yield, where no methyl group transfer has occurred. Reaction of alcohol with [Cl(2)Ga{N(SiMe(3))(2)}](2) was then found to yield [Cl(2)Ga(OR)](2) (8, R = CH(2)CH(2)NMe(2)), and further reaction of 8 with LiN(SiMe(3))(2) yielded the gallium amido alkoxide complex, [ClGa{N(SiMe(3))(2)}(OR)](2) (9, R = CH(2)CH(2)NMe(2)), similar to 6. The structures of compounds 4, 5, 7, and 8 have been determined by single-crystal X-ray diffraction.

MODs vs. NPs: Vying for the Future of Printed Electronics

“…Inspired by the Ag atomic layer deposition field, Black et al used the metal-organic compound: [(hfac)(1,5-COD)Ag] (where hfac = hexafluoroacetylacetone) in their MOD ink. Acetylacetones [37] and their fluorinated counterparts are commonly found in vapour deposition techniques of metals and metal oxide, [38,39] but are rarely used in MOD ink chemistry. The hfac compound was dissolved in anhydrous toluene followed by the addition of isopropanol under inert conditions, producing a series of inks with varying organometallic/alcohol ink ratios.…”

Solution based CVD of main group materials

“…148,149 Within the remit of 'alkoxide' are a number of subdivisions, including the simpler monodentate alkoxides (e.g. 150 The precursors were synthesized via a 1 : 1 reaction of GaMe 3 with a donor-functionalised alcohol to yield the gallium mono-alkoxides, [Me 2 Ga(OCH 2 -CH 2 YR x )] 2 . 145 Whilst there are a number of variants to these donor-functionalised ligands, which improve solubility for use in AACVD and volatility for use in other types of CVD, carbon contamination is kept to a minimum with the use of shorter chains.…”

Precursors for Atmospheric Plasma‐Enhanced Sintering: Low‐Temperature Inkjet Printing of Conductive Copper

“…Indeed, the production of solid and stable MOD inks would considerably improve the inkjet printing of conductive features by preventing excessive and detrimental wetting of the substrates, including paper, as well as early decomposition . From the coordination of bidentate diamine and amino‐alcohol ligands with copper(II) nitrate to produce isolated precursors, this work aims to contribute toward a greater understanding of the relationship between functionality of ligands and resultant ink performance, with the hope that this new knowledge will assist in the selection of more effective directions for the development of ink precursors for the low‐temperature plasma‐enhanced sintering of highly conductive metallic features . These new isolated copper precursors, which are solid, water‐soluble, and stable under ambient conditions, have been investigated with the atmospheric‐pressure plasma‐assisted inkjet printing that was recently demonstrated as a versatile room‐temperature approach that can be upscaled for the immediate conversion of MOD inks (Scheme ) …”