Syntheses and Structures of [Sn{NR}2{Sn(μ-NMe2)}2]: Model Intermediates in the Formation of Imido Group 14 Cages and Rings [R = 2,6-Pr2iC6H3 (Dipp), 2,4,6-Me3C6H2 (Mes)]

Robert E. Allan; Michael A. Beswick; Georgina R. Coggan; Paul R. Raithby; Andrew E.H. Wheatley; Dominic S. Wright

doi:10.1021/ic970336i

Syntheses and Structures of [Sn{NR}₂{Sn(μ-NMe₂)}₂]: Model Intermediates in the Formation of Imido Group 14 Cages and Rings [R = 2,6-Pr₂ⁱC₆H₃ (Dipp), 2,4,6-Me₃C₆H₂ (Mes)]

Robert E. Allan, Michael A. Beswick, Georgina R. Coggan, Paul R. Raithby, Andrew E.H. Wheatley, Dominic S. Wright

University of Cambridge

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16 Citations (SciVal)

Abstract

The 1:1 reactions of aliphatic primary amines [RNH₂] with [Sn(NMe₂)₂] yield the imido Sn(II) cubanes [SnNR]₄; however, for highly sterically crowded amines this reaction is retarded and the model intermediates [Sn{NR}₂-{Sn(μ-NMe₂)}₂] [R = 2,6-PrⁱC₆H₃ (Dipp) (1), 2,4,6-Me₃C₆H₂ (Mes) (2)] can be isolated. The latter indicate that the formation of imido cubanes and trimers from the metalation reactions of primary amines with a range of group 14 precursors may occur via a common reaction sequence involving stepwise metalation. The low-temperature X-ray structures of 1 and 2 show them to have similar [Sn₃N₄] cage arrangements consisting of a planar {Sn(NR)₂} unit straddling a {Sn(μ-NMe₂)}₂ ring. No intermolecular association occurs in the solid-state structure of 1. However, the reduced steric demands of the Mes groups in 2 lead to a complicated three-dimensional network consisting of fused hexameric units linked by Sn⋯Sn interactions.

Original language	English
Pages (from-to)	5202-5205
Number of pages	4
Journal	Inorganic Chemistry
Volume	36
Issue number	23
DOIs	https://doi.org/10.1021/ic970336i
Publication status	Published - 5 Nov 1997

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Syntheses and Structures of [Sn{NR}₂{Sn(μ-NMe₂)}₂]: Model Intermediates in the Formation of Imido Group 14 Cages and Rings [R = 2,6-Pr₂ⁱC₆H₃ (Dipp), 2,4,6-Me₃C₆H₂ (Mes)]. / Allan, Robert E.; Beswick, Michael A.; Coggan, Georgina R. et al.
In: Inorganic Chemistry, Vol. 36, No. 23, 05.11.1997, p. 5202-5205.

Research output: Contribution to journal › Article › peer-review

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title = "Syntheses and Structures of [Sn{NR}2{Sn(μ-NMe2)}2]: Model Intermediates in the Formation of Imido Group 14 Cages and Rings [R = 2,6-Pr2iC6H3 (Dipp), 2,4,6-Me3C6H2 (Mes)]",

abstract = "The 1:1 reactions of aliphatic primary amines [RNH2] with [Sn(NMe2)2] yield the imido Sn(II) cubanes [SnNR]4; however, for highly sterically crowded amines this reaction is retarded and the model intermediates [Sn{NR}2-{Sn(μ-NMe2)}2] [R = 2,6-PriC6H3 (Dipp) (1), 2,4,6-Me3C6H2 (Mes) (2)] can be isolated. The latter indicate that the formation of imido cubanes and trimers from the metalation reactions of primary amines with a range of group 14 precursors may occur via a common reaction sequence involving stepwise metalation. The low-temperature X-ray structures of 1 and 2 show them to have similar [Sn3N4] cage arrangements consisting of a planar {Sn(NR)2} unit straddling a {Sn(μ-NMe2)}2 ring. No intermolecular association occurs in the solid-state structure of 1. However, the reduced steric demands of the Mes groups in 2 lead to a complicated three-dimensional network consisting of fused hexameric units linked by Sn⋯Sn interactions.",

author = "Allan, {Robert E.} and Beswick, {Michael A.} and Coggan, {Georgina R.} and Raithby, {Paul R.} and Wheatley, {Andrew E.H.} and Wright, {Dominic S.}",

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T2 - Model Intermediates in the Formation of Imido Group 14 Cages and Rings [R = 2,6-Pr2iC6H3 (Dipp), 2,4,6-Me3C6H2 (Mes)]

AU - Allan, Robert E.

AU - Beswick, Michael A.

AU - Coggan, Georgina R.

AU - Raithby, Paul R.

AU - Wheatley, Andrew E.H.

AU - Wright, Dominic S.

PY - 1997/11/5

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N2 - The 1:1 reactions of aliphatic primary amines [RNH2] with [Sn(NMe2)2] yield the imido Sn(II) cubanes [SnNR]4; however, for highly sterically crowded amines this reaction is retarded and the model intermediates [Sn{NR}2-{Sn(μ-NMe2)}2] [R = 2,6-PriC6H3 (Dipp) (1), 2,4,6-Me3C6H2 (Mes) (2)] can be isolated. The latter indicate that the formation of imido cubanes and trimers from the metalation reactions of primary amines with a range of group 14 precursors may occur via a common reaction sequence involving stepwise metalation. The low-temperature X-ray structures of 1 and 2 show them to have similar [Sn3N4] cage arrangements consisting of a planar {Sn(NR)2} unit straddling a {Sn(μ-NMe2)}2 ring. No intermolecular association occurs in the solid-state structure of 1. However, the reduced steric demands of the Mes groups in 2 lead to a complicated three-dimensional network consisting of fused hexameric units linked by Sn⋯Sn interactions.

AB - The 1:1 reactions of aliphatic primary amines [RNH2] with [Sn(NMe2)2] yield the imido Sn(II) cubanes [SnNR]4; however, for highly sterically crowded amines this reaction is retarded and the model intermediates [Sn{NR}2-{Sn(μ-NMe2)}2] [R = 2,6-PriC6H3 (Dipp) (1), 2,4,6-Me3C6H2 (Mes) (2)] can be isolated. The latter indicate that the formation of imido cubanes and trimers from the metalation reactions of primary amines with a range of group 14 precursors may occur via a common reaction sequence involving stepwise metalation. The low-temperature X-ray structures of 1 and 2 show them to have similar [Sn3N4] cage arrangements consisting of a planar {Sn(NR)2} unit straddling a {Sn(μ-NMe2)}2 ring. No intermolecular association occurs in the solid-state structure of 1. However, the reduced steric demands of the Mes groups in 2 lead to a complicated three-dimensional network consisting of fused hexameric units linked by Sn⋯Sn interactions.

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Syntheses and Structures of [Sn{NR}₂{Sn(μ-NMe₂)}₂]: Model Intermediates in the Formation of Imido Group 14 Cages and Rings [R = 2,6-Pr₂ⁱC₆H₃ (Dipp), 2,4,6-Me₃C₆H₂ (Mes)]

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