Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes)
Heterobimetallic derivatives of a bis(carborane), [μ<sub>7,8</sub>-(1′,3′−3′-Cl-3′-PPh<sub>3</sub>-<i>closo</i>-3′,1′,2′-RhC<sub>2</sub>B<sub>9</sub>H&...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2020-01-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/25/3/519 |
| id |
doaj-4188d91636984935855c21e4a1e83369 |
|---|---|
| record_format |
Article |
| spelling |
doaj-4188d91636984935855c21e4a1e833692020-11-25T02:18:25ZengMDPI AGMolecules1420-30492020-01-0125351910.3390/molecules25030519molecules25030519Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes)Antony P. Y. Chan0Georgina M. Rosair1Alan J. Welch2Institute of Chemical Sciences, School of Engineering & Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKInstitute of Chemical Sciences, School of Engineering & Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKInstitute of Chemical Sciences, School of Engineering & Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKHeterobimetallic derivatives of a bis(carborane), [μ<sub>7,8</sub>-(1′,3′−3′-Cl-3′-PPh<sub>3</sub>-<i>closo</i>-3′,1′,2′-RhC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)-2-(<i>p</i>-cymene)-<i>closo</i>-2,1,8-RuC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>] (<b>1</b>) and [μ<sub>7,8</sub>-(1′,3′−3′-Cl-3′-PPh<sub>3</sub>-<i>closo</i>-3′,1′,2′-RhC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)-2-Cp-<i>closo</i>-2,1,8-CoC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>] (<b>2</b>) have been synthesised and characterised, including crystallographic studies. A minor co-product during the synthesis of compound <b>2</b> is the new species [8-{8′-2′-H-2′,2′-(PPh<sub>3</sub>)<sub>2</sub>-<i>closo</i>-2′,1′,8′-RhC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>}-2-Cp-<i>closo</i>-2,1,8-CoC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>] (<b>3</b>), isolated as a mixture of diastereoisomers. Although, in principle, compounds <b>1</b> and <b>2</b> could also exist as two diastereoisomers, only one (the same in both cases) is formed. It is suggested that the preferred exopolyhedral ligand orientation in the rhodacarboranes in the non-observed diastereoisomers would lead to unacceptable steric crowding between the PPh<sub>3</sub> ligand and either the <i>p</i>-cymene (compound <b>1</b>) or Cp (compound <b>2</b>) ligand of the ruthenacarborane or cobaltacarborane, respectively.https://www.mdpi.com/1420-3049/25/3/519carboranemetallacarboranediastereoisomersteric crowding |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Antony P. Y. Chan Georgina M. Rosair Alan J. Welch |
| spellingShingle |
Antony P. Y. Chan Georgina M. Rosair Alan J. Welch Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes) Molecules carborane metallacarborane diastereoisomer steric crowding |
| author_facet |
Antony P. Y. Chan Georgina M. Rosair Alan J. Welch |
| author_sort |
Antony P. Y. Chan |
| title |
Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes) |
| title_short |
Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes) |
| title_full |
Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes) |
| title_fullStr |
Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes) |
| title_full_unstemmed |
Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(Carboranes) |
| title_sort |
exopolyhedral ligand orientation controls diastereoisomer in mixed-metal bis(carboranes) |
| publisher |
MDPI AG |
| series |
Molecules |
| issn |
1420-3049 |
| publishDate |
2020-01-01 |
| description |
Heterobimetallic derivatives of a bis(carborane), [μ<sub>7,8</sub>-(1′,3′−3′-Cl-3′-PPh<sub>3</sub>-<i>closo</i>-3′,1′,2′-RhC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)-2-(<i>p</i>-cymene)-<i>closo</i>-2,1,8-RuC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>] (<b>1</b>) and [μ<sub>7,8</sub>-(1′,3′−3′-Cl-3′-PPh<sub>3</sub>-<i>closo</i>-3′,1′,2′-RhC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>)-2-Cp-<i>closo</i>-2,1,8-CoC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>] (<b>2</b>) have been synthesised and characterised, including crystallographic studies. A minor co-product during the synthesis of compound <b>2</b> is the new species [8-{8′-2′-H-2′,2′-(PPh<sub>3</sub>)<sub>2</sub>-<i>closo</i>-2′,1′,8′-RhC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>}-2-Cp-<i>closo</i>-2,1,8-CoC<sub>2</sub>B<sub>9</sub>H<sub>10</sub>] (<b>3</b>), isolated as a mixture of diastereoisomers. Although, in principle, compounds <b>1</b> and <b>2</b> could also exist as two diastereoisomers, only one (the same in both cases) is formed. It is suggested that the preferred exopolyhedral ligand orientation in the rhodacarboranes in the non-observed diastereoisomers would lead to unacceptable steric crowding between the PPh<sub>3</sub> ligand and either the <i>p</i>-cymene (compound <b>1</b>) or Cp (compound <b>2</b>) ligand of the ruthenacarborane or cobaltacarborane, respectively. |
| topic |
carborane metallacarborane diastereoisomer steric crowding |
| url |
https://www.mdpi.com/1420-3049/25/3/519 |
| work_keys_str_mv |
AT antonypychan exopolyhedralligandorientationcontrolsdiastereoisomerinmixedmetalbiscarboranes AT georginamrosair exopolyhedralligandorientationcontrolsdiastereoisomerinmixedmetalbiscarboranes AT alanjwelch exopolyhedralligandorientationcontrolsdiastereoisomerinmixedmetalbiscarboranes |
| _version_ |
1724882310470303744 |