The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

Chadha, Raj K.; Chehayber, Jaafar M.; Drake, John E.

doi:10.1007/bf01185717

Cited by 14 publications

(12 citation statements)

References 11 publications

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“…The differences between the independent molecules appear to be due to solid-state packing effects; there are no significant intermolecular Sb•••X contacts. 6 The d(B−X) (X = Cl, Br, I) distances are not significantly different from those in [BX 3 (PMe 3 )], 51 [BBr 3 (P n Pr 3 )], 46 or [BX 3 (AsMe 3 )], 52 while the increase in d(B−E) (E = P, As, Sb) bond lengths corresponds to the increasing covalent radius of the pnictogen. 53 The d(B−Sb) bond lengths are rather similar but show a small decrease overall from Cl > Br > I, which agrees with the predicted Lewis acidity trend of the three trihalides.…”

Section: ■ Results and Discussionmentioning

confidence: 90%

Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding

2018

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The reaction of BX 3 (X = Cl, Br, I) with SbR 3 (R = Et, i Pr) in anhydrous hexane or toluene produced moisture-sensitive [BX 3 (SbR 3)], whose stability increases with halide: Cl < Br < I. Unstable [BF 3 (SbR 3)] species were also characterized spectroscopically but lose BF 3 very readily. The [MX 3 (SbR 3)] (M = Al, Ga, In) complexes were isolated from hexane solution; the Ga and In complexes can be recrystallized unchanged from CH 2 Cl 2 , but [AlX′ 3 (SbR 3)] (X′ = Br, I) undergoes X′/Cl exchange with the solvent. The new complexes were characterized by IR and multinuclear NMR spectroscopy (1 H, 13 C{ 1 H}, 11 B, 27 Al, 71 Ga, 115 In, as appropriate). X-ray crystal structures are reported for [BX 3 (SbR 3)] (X = Br, I; R = Et, i Pr; X = Cl, R = i Pr), [AlI 3 (Sb i Pr 3)], [GaX 3 (SbR 3)] (X = Cl, I; R = i Pr), [GaBr 3 (SbEt 3)], and [InX 3 (SbR 3)] (X = Cl, I; R = Et, i Pr); all contain pseudotetrahedral geometries at both the group 13 and antimony atoms, and comparisons with phosphine and arsine analogues are discussed. The donor−acceptor bond lengths are unexceptional, but coordination of the stibine is accompanied by a significant widening of the C−Sb−C angles and a small reduction in C−Sb distances. DFT calculations confirm these results from significant changes in the antimony 5s and 5p contributions to the Sb−C bonds, with corresponding increases in the 5p character of the antimony-based "lone pair" on coordination. Intermolecular hypervalent Cl•••Sb interactions are present in the two [InCl 3 (SbR 3)] complexes but absent in the others.

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Section: ■ Results and Discussionmentioning

confidence: 90%

Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding

2018

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“…Neither showed any BF coupling, consistent with fast exchange in solution; the spectra were unchanged at 180 K. The instability prevented growth of crystals for an X-ray study, although structures are known for the other three [BX3(AsMe3)] (X = Cl, Br or I). 22 …”

Section: Figurementioning

confidence: 99%

Systematics of BX₃ and BX₂⁺ Complexes (X = F, Cl, Br, I) with Neutral Diphosphine and Diarsine Ligands

et al. 2016

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“…Boron trihalides form 1:1 complexes with phosphine and arsine ligands, usually made by combination of the constituents in an inert solvent; hexane, benzene or toluene are the most commonly used, or sometimes in the absence of a solvent [113][114][115][116][117][118][119][120][121][122][123][124][125][126]. Table 5 lists structural data on typical examples.…”

Section: Boronmentioning

confidence: 99%

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

Burt

Levason

Reid

2014

Coordination Chemistry Reviews

104

137

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The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

Cited by 14 publications

References 11 publications

Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding

Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding

Systematics of BX₃ and BX₂⁺ Complexes (X = F, Cl, Br, I) with Neutral Diphosphine and Diarsine Ligands

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

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The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

Cited by 14 publications

References 11 publications

Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding

Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding

Systematics of BX3 and BX2+ Complexes (X = F, Cl, Br, I) with Neutral Diphosphine and Diarsine Ligands

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

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Systematics of BX₃ and BX₂⁺ Complexes (X = F, Cl, Br, I) with Neutral Diphosphine and Diarsine Ligands