[Rh(cod)Cl]2-catalysed hydrosilylation of hex-1-yne with Et3SiH in EtOH or DMF is highly selective for the formation of (Z)-vinylsilane, whereas [Rh(cod)Cl]2-PPh3 in MeCN or PrnCN is highly selective for the formation of (E)-vinylsilane; the active species for cis addition has been revealed to be RhI cationic complex generated in situ.
R. Takeuchi and N. Tanouchi, J. Chem. Soc., Chem. Commun., 1993, 1319 DOI: 10.1039/C39930001319
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