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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
Trialkylstibine complexes of boron, aluminum, gallium, and indium trihalides: synthesis, properties, and bonding
The reaction of BX3 (X = Cl, Br, I) with SbR3 (R = Et,iPr) in anhydrous hexane or toluene produced moisture-sensitive [BX3(SbR3)], whose stability increases with halide: Cl < Br < I. Unstable [BF3(SbR3)] species were also characterized spectroscopically but lose BF3 very readily. The [MX3(SbR3)] (M = Al, Ga, In) complexes were isolated from hexane solution; the Ga and In complexes can be recrystallized unchanged from CH2Cl2, but [AlX′3(SbR3)] (X′ = Br, I) undergoes X′/Cl exchange with the solvent. The new complexes were characterized by IR and multinuclear NMR spectroscopy (1H, 13C{1H}, 11B, 27Al, 71Ga, 115In, as appropriate). X-ray crystal structures are reported for [BX3(SbR3)] (X = Br, I; R = Et, iPr; X = Cl, R = iPr), [AlI3(SbiPr3)], [GaX3(SbR3)] (X = Cl, I; R = iPr), [GaBr3(SbEt3)], and [InX3(SbR3)] (X = Cl, I; R = Et, iPr); 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 [InCl3(SbR3)] complexes but absent in the others.
0276-7333
2123-2135
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Greenacre, Victoria, Levason, William and Reid, Gillian (2018) Trialkylstibine complexes of boron, aluminum, gallium, and indium trihalides: synthesis, properties, and bonding. Organometallics, 37 (13), 2123-2135. (doi:10.1021/acs.organomet.8b00265).

Record type: Article

Abstract

The reaction of BX3 (X = Cl, Br, I) with SbR3 (R = Et,iPr) in anhydrous hexane or toluene produced moisture-sensitive [BX3(SbR3)], whose stability increases with halide: Cl < Br < I. Unstable [BF3(SbR3)] species were also characterized spectroscopically but lose BF3 very readily. The [MX3(SbR3)] (M = Al, Ga, In) complexes were isolated from hexane solution; the Ga and In complexes can be recrystallized unchanged from CH2Cl2, but [AlX′3(SbR3)] (X′ = Br, I) undergoes X′/Cl exchange with the solvent. The new complexes were characterized by IR and multinuclear NMR spectroscopy (1H, 13C{1H}, 11B, 27Al, 71Ga, 115In, as appropriate). X-ray crystal structures are reported for [BX3(SbR3)] (X = Br, I; R = Et, iPr; X = Cl, R = iPr), [AlI3(SbiPr3)], [GaX3(SbR3)] (X = Cl, I; R = iPr), [GaBr3(SbEt3)], and [InX3(SbR3)] (X = Cl, I; R = Et, iPr); 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 [InCl3(SbR3)] complexes but absent in the others.

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SbR3group13 final revised 31_05_2018 unhighlighted - Accepted Manuscript
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Accepted/In Press date: 18 June 2018
e-pub ahead of print date: 18 June 2018
Published date: 26 June 2018

Identifiers

Local EPrints ID: 421739
URI: http://eprints.soton.ac.uk/id/eprint/421739
ISSN: 0276-7333
PURE UUID: a3265564-83d0-481b-8ad6-60bc5a2ebead
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 26 Jun 2018 16:30
Last modified: 18 Feb 2021 16:34

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Author: Victoria Greenacre
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD

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