Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligands

Brian Alexander Chalmers; Michael Buehl; Phillip Nejman; Alexandra Martha Zoya Slawin; J Derek Woollins; Petr Kilian

doi:10.1016/j.jorganchem.2015.09.006

Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligands

Brian Alexander Chalmers, Michael Buehl, Phillip Nejman, Alexandra Martha Zoya Slawin, J Derek Woollins, Petr Kilian

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

Abstract

The syntheses of rhodium(III) and iridium(III) half sandwich complexes containing tertiary arsine and stibine ligands of the form [Cp*M(L)Cl₂] (M = Rh, Ir; L = AsEt₃, AsPh₃, SbPh₃) are reported. These compounds represent infrequent examples of rhodium and iridium metal complexes bearing arsenic or antimony ligands. All new compounds were fully characterised using ¹H and ¹³C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. DFT calculations show the formation of the complexes from (Cp*MCl₂)₂ and EPh₃ (E = P, As, Sb) to be highly exothermic, although the enthalpic driving force is decreasing in the expected sequence P > As > Sb.

Original language	English
Journal	Journal of Organometallic Chemistry
Volume	In press
Early online date	8 Sept 2015
DOIs	https://doi.org/10.1016/j.jorganchem.2015.09.006
Publication status	Published - 2015

Keywords

Arsine
Stibine
Rhodium
Iridium
Half-sandwich complex
DFT calculations

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10.1016/j.jorganchem.2015.09.006

Kilian_2015_JOC_Rhodium_AM
Copyright © 2015 Published by Elsevier B.V. This work is 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://dx.doi.org/10.1016/j.jorganchem.2015.09.006
Accepted author manuscript, 1.8 MB

Cite this

@article{b62347ecddc543f29f4927c32bd38a2d,

title = "Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligands",

abstract = "The syntheses of rhodium(III) and iridium(III) half sandwich complexes containing tertiary arsine and stibine ligands of the form [Cp*M(L)Cl2] (M = Rh, Ir; L = AsEt3, AsPh3, SbPh3) are reported. These compounds represent infrequent examples of rhodium and iridium metal complexes bearing arsenic or antimony ligands. All new compounds were fully characterised using 1H and 13C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. DFT calculations show the formation of the complexes from (Cp*MCl2)2 and EPh3 (E = P, As, Sb) to be highly exothermic, although the enthalpic driving force is decreasing in the expected sequence P > As > Sb.",

keywords = "Arsine, Stibine, Rhodium, Iridium, Half-sandwich complex, DFT calculations",

author = "Chalmers, {Brian Alexander} and Michael Buehl and Phillip Nejman and Slawin, {Alexandra Martha Zoya} and Woollins, {J Derek} and Petr Kilian",

note = "This work was financially supported by the EPSRC and the EPSRC National Mass Spectrometry Service Centre (NMSSC) Swansea. ",

year = "2015",

doi = "10.1016/j.jorganchem.2015.09.006",

language = "English",

volume = "In press",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

}

TY - JOUR

T1 - Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligands

AU - Chalmers, Brian Alexander

AU - Buehl, Michael

AU - Nejman, Phillip

AU - Slawin, Alexandra Martha Zoya

AU - Woollins, J Derek

AU - Kilian, Petr

N1 - This work was financially supported by the EPSRC and the EPSRC National Mass Spectrometry Service Centre (NMSSC) Swansea.

PY - 2015

Y1 - 2015

N2 - The syntheses of rhodium(III) and iridium(III) half sandwich complexes containing tertiary arsine and stibine ligands of the form [Cp*M(L)Cl2] (M = Rh, Ir; L = AsEt3, AsPh3, SbPh3) are reported. These compounds represent infrequent examples of rhodium and iridium metal complexes bearing arsenic or antimony ligands. All new compounds were fully characterised using 1H and 13C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. DFT calculations show the formation of the complexes from (Cp*MCl2)2 and EPh3 (E = P, As, Sb) to be highly exothermic, although the enthalpic driving force is decreasing in the expected sequence P > As > Sb.

AB - The syntheses of rhodium(III) and iridium(III) half sandwich complexes containing tertiary arsine and stibine ligands of the form [Cp*M(L)Cl2] (M = Rh, Ir; L = AsEt3, AsPh3, SbPh3) are reported. These compounds represent infrequent examples of rhodium and iridium metal complexes bearing arsenic or antimony ligands. All new compounds were fully characterised using 1H and 13C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. DFT calculations show the formation of the complexes from (Cp*MCl2)2 and EPh3 (E = P, As, Sb) to be highly exothermic, although the enthalpic driving force is decreasing in the expected sequence P > As > Sb.

KW - Arsine

KW - Stibine

KW - Rhodium

KW - Iridium

KW - Half-sandwich complex

KW - DFT calculations

UR - http://www.sciencedirect.com/science/article/pii/S0022328X15301352#appd001

U2 - 10.1016/j.jorganchem.2015.09.006

DO - 10.1016/j.jorganchem.2015.09.006

M3 - Article

SN - 0022-328X

VL - In press

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligands

Abstract

Keywords

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