Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium

Michael Trose; Stuart Burnett; Simon J. Bonyhady; Cameron Jones; David B. Cordes; Alexandra M. Z. Slawin; Andreas Stasch

doi:10.1039/C8DT01798K

Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium

Michael Trose, Stuart Burnett, Simon J. Bonyhady, Cameron Jones, David B. Cordes, Alexandra M. Z. Slawin, Andreas Stasch

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

Abstract

The mixed N-heterocyclic carbene (NHC) complexes NHCAlH_xI_3-x, where NHC is IDip or IMes ((HCNAr)₂C:, Ar = 2,6-iPr₂C₆H₃ = Dip (IDip); or 2,4,6-Me₃C₆H₂ = Mes (IMes)), x = 1 or 2, were either prepared from NHCAlH3 and NHCAlI3 or by halogenation of NHCAlH₃ with MeI. Reaction of [(IDip)AlH_xI_3-x], with x = 0-3, with another equivalent of a IDip afforded either fluxional equilibria in benzene solution for x = 0, no reaction for x = 3, or the new mixed normal-abnormal NHC-coordinated ionic complexes [(IDip)AlH₂(aIDip)]I (9) and [(IDip)AlHI(aIDip)]I (10), where aIDip is the abnormal IDip carbene tautomer bonded through its 4-position. The molecular structures of 9 and 10 were determined and show slightly shorter Al–C(aIDip) than Al–C(IDip) distances. In addition, a complex containing [(IDip)AlI2(aIDip)]I (11) was structurally characterized though could not intentionally be synthesised. Possible formation mechanisms for 9-11 are discussed and the normal and abnormal IDip coordination to the aluminium(III) centre is believed to occur for steric reasons.

Original language	English
Journal	Dalton Transactions
Volume	In press
Early online date	11 Jul 2018
DOIs	https://doi.org/10.1039/C8DT01798K
Publication status	E-pub ahead of print - 11 Jul 2018

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Trose_2018_DT_NormalAbnormal_AAM
© 2018 The Author(s). This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1039/C8DT01798K
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Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium (dataset)
Trose, M. (Creator), Burnett, S. (Creator), Bonyhady, S. J. (Creator), Jones, C. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator) & Stasch, A. (Creator), Cambridge Crystallographic Data Centre, 19 Jul 2018
https://dx.doi.org/10.5517/ccdc.csd.cc1zs946 and 3 more links, https://dx.doi.org/10.5517/ccdc.csd.cc1zs957, https://dx.doi.org/10.5517/ccdc.csd.cc1zs968, https://dx.doi.org/10.5517/ccdc.csd.cc1zs979 (show fewer)
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@article{98590b8e1d884187a1b3b85783196d81,

title = "Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium",

abstract = "The mixed N-heterocyclic carbene (NHC) complexes NHCAlHxI3-x, where NHC is IDip or IMes ((HCNAr)2C:, Ar = 2,6-iPr2C6H3 = Dip (IDip); or 2,4,6-Me3C6H2 = Mes (IMes)), x = 1 or 2, were either prepared from NHCAlH3 and NHCAlI3 or by halogenation of NHCAlH3 with MeI. Reaction of [(IDip)AlHxI3-x], with x = 0-3, with another equivalent of a IDip afforded either fluxional equilibria in benzene solution for x = 0, no reaction for x = 3, or the new mixed normal-abnormal NHC-coordinated ionic complexes [(IDip)AlH2(aIDip)]I (9) and [(IDip)AlHI(aIDip)]I (10), where aIDip is the abnormal IDip carbene tautomer bonded through its 4-position. The molecular structures of 9 and 10 were determined and show slightly shorter Al–C(aIDip) than Al–C(IDip) distances. In addition, a complex containing [(IDip)AlI2(aIDip)]I (11) was structurally characterized though could not intentionally be synthesised. Possible formation mechanisms for 9-11 are discussed and the normal and abnormal IDip coordination to the aluminium(III) centre is believed to occur for steric reasons.",

author = "Michael Trose and Stuart Burnett and Bonyhady, {Simon J.} and Cameron Jones and Cordes, {David B.} and Slawin, {Alexandra M. Z.} and Andreas Stasch",

note = "We thank the University of St Andrews and the EPSRC UK National Mass Spectrometry Facility (NMSF) at Swansea University.",

year = "2018",

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day = "11",

doi = "10.1039/C8DT01798K",

language = "English",

volume = "In press",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "ROYAL SOC CHEMISTRY",

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TY - JOUR

T1 - Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium

AU - Trose, Michael

AU - Burnett, Stuart

AU - Bonyhady, Simon J.

AU - Jones, Cameron

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Stasch, Andreas

N1 - We thank the University of St Andrews and the EPSRC UK National Mass Spectrometry Facility (NMSF) at Swansea University.

PY - 2018/7/11

Y1 - 2018/7/11

N2 - The mixed N-heterocyclic carbene (NHC) complexes NHCAlHxI3-x, where NHC is IDip or IMes ((HCNAr)2C:, Ar = 2,6-iPr2C6H3 = Dip (IDip); or 2,4,6-Me3C6H2 = Mes (IMes)), x = 1 or 2, were either prepared from NHCAlH3 and NHCAlI3 or by halogenation of NHCAlH3 with MeI. Reaction of [(IDip)AlHxI3-x], with x = 0-3, with another equivalent of a IDip afforded either fluxional equilibria in benzene solution for x = 0, no reaction for x = 3, or the new mixed normal-abnormal NHC-coordinated ionic complexes [(IDip)AlH2(aIDip)]I (9) and [(IDip)AlHI(aIDip)]I (10), where aIDip is the abnormal IDip carbene tautomer bonded through its 4-position. The molecular structures of 9 and 10 were determined and show slightly shorter Al–C(aIDip) than Al–C(IDip) distances. In addition, a complex containing [(IDip)AlI2(aIDip)]I (11) was structurally characterized though could not intentionally be synthesised. Possible formation mechanisms for 9-11 are discussed and the normal and abnormal IDip coordination to the aluminium(III) centre is believed to occur for steric reasons.

AB - The mixed N-heterocyclic carbene (NHC) complexes NHCAlHxI3-x, where NHC is IDip or IMes ((HCNAr)2C:, Ar = 2,6-iPr2C6H3 = Dip (IDip); or 2,4,6-Me3C6H2 = Mes (IMes)), x = 1 or 2, were either prepared from NHCAlH3 and NHCAlI3 or by halogenation of NHCAlH3 with MeI. Reaction of [(IDip)AlHxI3-x], with x = 0-3, with another equivalent of a IDip afforded either fluxional equilibria in benzene solution for x = 0, no reaction for x = 3, or the new mixed normal-abnormal NHC-coordinated ionic complexes [(IDip)AlH2(aIDip)]I (9) and [(IDip)AlHI(aIDip)]I (10), where aIDip is the abnormal IDip carbene tautomer bonded through its 4-position. The molecular structures of 9 and 10 were determined and show slightly shorter Al–C(aIDip) than Al–C(IDip) distances. In addition, a complex containing [(IDip)AlI2(aIDip)]I (11) was structurally characterized though could not intentionally be synthesised. Possible formation mechanisms for 9-11 are discussed and the normal and abnormal IDip coordination to the aluminium(III) centre is believed to occur for steric reasons.

U2 - 10.1039/C8DT01798K

DO - 10.1039/C8DT01798K

M3 - Article

SN - 1477-9226

VL - In press

JO - Dalton Transactions

JF - Dalton Transactions

ER -

Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium

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Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium (dataset)

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