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Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(carboranes).


ABSTRACT: Heterobimetallic derivatives of a bis(carborane), [?7,8-(1',3'-3'-Cl-3'-PPh3-closo-3',1',2'-RhC2B9H10)-2-(p-cymene)-closo-2,1,8-RuC2B9H10] (1) and [?7,8-(1',3'-3'-Cl-3'-PPh3-closo-3',1',2'-RhC2B9H10)-2-Cp-closo-2,1,8-CoC2B9H10] (2) have been synthesised and characterised, including crystallographic studies. A minor co-product during the synthesis of compound 2 is the new species [8-{8'-2'-H-2',2'-(PPh3)2-closo-2',1',8'-RhC2B9H10}-2-Cp-closo-2,1,8-CoC2B9H10] (3), isolated as a mixture of diastereoisomers. Although, in principle, compounds 1 and 2 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 PPh3 ligand and either the p-cymene (compound 1) or Cp (compound 2) ligand of the ruthenacarborane or cobaltacarborane, respectively.

SUBMITTER: Chan APY 

PROVIDER: S-EPMC7037510 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(carboranes).

Chan Antony P Y APY   Rosair Georgina M GM   Welch Alan J AJ  

Molecules (Basel, Switzerland) 20200124 3


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, in  ...[more]

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