A d10 Ag(i) amine-borane σ-complex and comparison with a d8 Rh(i) analogue: structures on the η1 to η2:η2 continuum

Alice Johnson; Antonio J. Martínez-Martínez; Stuart A. Macgregor; Andrew S. Weller

doi:10.1039/c9dt00971j

A d10 Ag(i) amine-borane σ-complex and comparison with a d8 Rh(i) analogue: structures on the η1 to η2:η2 continuum

Alice Johnson, Antonio J. Martínez-Martínez, Stuart A. Macgregor, Andrew S. Weller

University of Oxford

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Abstract

H3B·NMe3 σ-complexes of d8 [(L1)Rh][BArF4] and d10 [(L1)Ag][BArF4] (where L1 = 2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine) have been prepared and structurally characterised. Analysis of the molecular and electronic structures reveal important but subtle differences in the nature of the bonding in these σ-complexes, which differ only by the identity of the metal centre and the d-electron count. With Rh the amine-borane binds in an η2:η2 fashion, whereas at Ag the unsymmetrical {AgH3B·NMe3} unit suggests a structure lying between the η2:η2 and η1 extremes.

Original language	English
Pages (from-to)	9776-9781
Number of pages	6
Journal	Dalton Transactions
Volume	48
Issue number	26
Early online date	23 Apr 2019
DOIs	https://doi.org/10.1039/c9dt00971j
Publication status	E-pub ahead of print - 23 Apr 2019

ASJC Scopus subject areas

Inorganic Chemistry

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title = "A d10 Ag(i) amine-borane σ-complex and comparison with a d8 Rh(i) analogue: structures on the η1 to η2:η2 continuum",

abstract = "H3B·NMe3 σ-complexes of d8 [(L1)Rh][BArF4] and d10 [(L1)Ag][BArF4] (where L1 = 2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine) have been prepared and structurally characterised. Analysis of the molecular and electronic structures reveal important but subtle differences in the nature of the bonding in these σ-complexes, which differ only by the identity of the metal centre and the d-electron count. With Rh the amine-borane binds in an η2:η2 fashion, whereas at Ag the unsymmetrical {AgH3B·NMe3} unit suggests a structure lying between the η2:η2 and η1 extremes.",

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T1 - A d10 Ag(i) amine-borane σ-complex and comparison with a d8 Rh(i) analogue

T2 - structures on the η1 to η2:η2 continuum

AU - Johnson, Alice

AU - Martínez-Martínez, Antonio J.

AU - Macgregor, Stuart A.

AU - Weller, Andrew S.

PY - 2019/4/23

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N2 - H3B·NMe3 σ-complexes of d8 [(L1)Rh][BArF4] and d10 [(L1)Ag][BArF4] (where L1 = 2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine) have been prepared and structurally characterised. Analysis of the molecular and electronic structures reveal important but subtle differences in the nature of the bonding in these σ-complexes, which differ only by the identity of the metal centre and the d-electron count. With Rh the amine-borane binds in an η2:η2 fashion, whereas at Ag the unsymmetrical {AgH3B·NMe3} unit suggests a structure lying between the η2:η2 and η1 extremes.

AB - H3B·NMe3 σ-complexes of d8 [(L1)Rh][BArF4] and d10 [(L1)Ag][BArF4] (where L1 = 2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine) have been prepared and structurally characterised. Analysis of the molecular and electronic structures reveal important but subtle differences in the nature of the bonding in these σ-complexes, which differ only by the identity of the metal centre and the d-electron count. With Rh the amine-borane binds in an η2:η2 fashion, whereas at Ag the unsymmetrical {AgH3B·NMe3} unit suggests a structure lying between the η2:η2 and η1 extremes.

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A d10 Ag(i) amine-borane σ-complex and comparison with a d8 Rh(i) analogue: structures on the η1 to η2:η2 continuum

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