Germanium and Tin Monoxides Trapped by Oxophilic Germylene and Stannylene Ligands

Gao, Yue; Yang, Ying; Zheng, Wenjun; Su, Yuanyuan; Zhang, Xiang; Roesky, Herbert W.

doi:10.1021/acs.inorgchem.7b00918

Cited by 10 publications

(12 citation statements)

References 46 publications

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“…We recently prepared a donor–acceptor complex of chloro‐oxoborane IPr⋅ClB=O⋅B(C 6 F 5 ) 3 by B(C 6 F 5 ) 3 ‐induced ClSiMe 3 loss from the dihalosiloxyborane adduct IPr⋅BCl 2 (OSiMe 3 ) (Scheme ). Accordingly, we reasoned that the hitherto unknown precursor IPr⋅GeCl(OSiMe 3 ) would be a suitable precursor to carbene‐stabilized GeO in the presence of a strong Lewis acid (Scheme ) …”

Section: Resultsmentioning

confidence: 99%

Neutral, Cationic and Hydride‐substituted Siloxygermylenes

Roy

Fujimori

Ferguson

et al. 2018

Chemistry A European J

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The introduction of the labile trimethylsiloxy group to Ge centers in the presence of an N-heterocyclic carbene donor is reported. The new complex IPr⋅GeCl(OSiMe ) (IPr=[(HCNDipp) C:]; Dipp=2,6-iPr C H ) was readily converted into the structurally unique Ge siloxy(hydrido)germylene IPr⋅GeH(OSiMe )⋅BH by treatment with lithium borohydride. Additionally, the reactive siloxygermylene cation [IPr⋅Ge(OSiMe )] was synthesized and clean oxidative addition of CH Cl was demonstrated. The two-coordinate [IPr⋅Ge(OSiMe )] cation also promoted the catalytic hydroborylation of sterically hindered ketones under mild conditions, with enhanced reactivity stemming from an open coordination site at Ge.

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Section: Resultsmentioning

confidence: 99%

Neutral, Cationic and Hydride‐substituted Siloxygermylenes

Roy

Fujimori

Ferguson

et al. 2018

Chemistry A European J

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“…Each Sn atom in 1 F was bound to a µ 3 -bridging oxygen atom with similar bond lengths and Sn -O -Sn angles close to 120°that sum to 359.4(2)°, a structural motif similar to the recently prepared "trapped" SnO complex A. 36 If analagous, then we can consider the stoichiometry of the complex to be {SnO…”

mentioning

confidence: 96%

“…Examples of trapped SnO are rare and often present as cages or clusters, [37][38][39][40] including the trifluoroacetic acid ligated derivative 1 F • HO 2 CCF 3 isolated upon decomposition of 1 . 31 Recently, two rationally synthesized molecular examples were achieved using an acyclic 3,5-di-tert-butyl-1,2,4diazaphospholide framework (A), 36 a tridentate pincer lutidinebridged benzannulated N-heterocyclic bis(stannylene) (B), 41 respectively, and can be compared to the imido heterocubane prepared by Veith and Lange (C, Chart 2). 37 However, there are significant differences between the Sn 3µ 3 -O bonding modes of A and 1 F .…”

mentioning

confidence: 99%

“…been previously discussed in detail. 36 ) The Sn 3 -O bond lengths in 1 F (Sn [1][2][3] -O5 and Sn [4][5][6] -O12) are longer than in B by about 0.01 Å, presumably due to the Sn atoms in the former being stabilized by their higher coordination number, diminishing the Lewis acidity of the Sn atom to the µ 3 -oxygen's lone pairs. Despite the similarities to B in the µ 3 -oxygen atoms O5 and O12 of 1 F , it is misleading to describe it as directly analogous to the previously observed "trapped" SnO species.…”

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confidence: 99%

“…Correlation matrices can be found in Tables S43 and S62, respectively. All amplitudes of vibration were refined as outlined in Ref 36…”

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confidence: 99%

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Supramolecular Organization and Evaporation of Polymeric Tin Trifluoroacetates

Bačić¹,

Rankine²,

Masuda³

et al. 2019

Preprint

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<div> <div> <div> <p>Simple tin carboxylates make up a family of important industrial catalysts and precursors for deposition of SnO2 thin films. However, their structures remain disparately characterized, and tin trifluoroacetates have been particularly elusive. Here we report on a combined X-ray diffraction (XRD), gas phase electron diffraction (GED) and density functional theory (DFT) study into the structure and bonding of tin(II) and tin(IV) trifluoroacetates to understand their influence on thermal stability and volatility. Tin(II) bis(trifluoroacetate) (1′) eliminates trifluoroacetic anhydride upon sublimation to form the linear polymeric hexatin(II)-di-μ -oxy-octakis-μ-trifluoroacetate (1F ), which itself sublimes (1 Torr at 191 C) as a 1:1 mixture of 1 and ditin(II)-μ-oxy-bis-μ-trifluoroacetate (1′′). Tin(IV) tetrakis(trifluoroacetate) (2F) is also polymeric in the solid state, but evaporates as a monomer at low temperatures (1 Torr at 84 ◦C). Together they make a family of multifunctional Lewis acidic and basic building blocks for supramolecular organization of clusters and polymers in the solid state. Anomalous trends in the volatility of these trifluoroacetates and their hydrogenated derivatives can be rationalized by consideration of their modes of polymerization with respect to the thermodynamics of evaporation. Both 1F and 2F combine high thermal stability and volatility, and are demonstrated to be complementary, safe, and green potential precursors for chemical vapor deposition (CVD) or atomic layer deposition (ALD) of earth-abundant transparent conducting F-doped SnO2. </p> <div><div><div> <p> </p> </div> </div> </div> </div> </div> </div>

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Synthesis, Characterization, and Reaction of Digermylenes

Huo

Zhang

et al. 2022

Chemistry An Asian Journal

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A series of digermylenes R(EGeL) 2 (L = CH[C(Me)N-(Ar)] 2 , Ar = 2,6-iPr 2 C 6 H 3 ; E = O, R = 1,3-C 6 H 4 (1), 1,4-C 6 H 4 (2), Me 2 C(CH 2 ) 2 (3); E = NH, R = 1,4-C 6 H 4 (4), 1,4-C 6 H 10 (5); E = C(O)O, R = 1,3-C 6 H 4 (6)) were synthesized by the reactions of L'Ge (L' = HC[C(CH 2 )N(Ar)]C(Me)N(Ar), Ar = 2,6-iPr 2 C 6 H 3 ) with selected diphenols, diol, diamines, and o-/m-phthalic acids, respectively. Treatment of digermylene 1,3-C 6 H 4 (OGeL) 2 (1) with sulfur, selenium and CuX (X = Cl, Br, I) led to the formation of 1,3-C 6 H 4 [OGe(S)L] 2 (8), 1,3-C 6 H 4 [OGe(Se)L] 2 (9), and (CuX) 2 [1,3-C 6 H 4 (OGeL) 2 ] 2 (X = Cl (10), Br (11), I ( 12)), respectively. The obtained products were characterized by melting point, elemental analysis, FT-IR, 1 H and 13 C NMR spectroscopy, and single-crystal X-ray diffraction.

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Germanium and Tin Monoxides Trapped by Oxophilic Germylene and Stannylene Ligands

Cited by 10 publications

References 46 publications

Neutral, Cationic and Hydride‐substituted Siloxygermylenes

Neutral, Cationic and Hydride‐substituted Siloxygermylenes

Supramolecular Organization and Evaporation of Polymeric Tin Trifluoroacetates

Synthesis, Characterization, and Reaction of Digermylenes

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