Reactions of an anionic chelate phosphane/borata-alkene ligand with [Rh(nbd)Cl] 2 , [Rh(CO) 2 Cl] 2 and [Ir(cod)Cl] 2

• Published in: Chemical science (Cambridge) Vol. 11; no. 28; pp. 7349 - 7355
• Main Authors: Watanabe, Kohei, Ueno, Atsushi, Tao, Xin, Škoch, Karel, Jie, Xiaoming, Vagin, Sergei, Rieger, Bernhard, Daniliuc, Constantin G, Letzel, Matthias C, Kehr, Gerald, Erker, Gerhard
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 28-07-2020
• Subjects: Alkenes; Anions; Carbon monoxide; Catalysts; Chelates; Crystallography; Dimers; Ligands; Rhodium; Transition metals
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/D0SC02223C

Borata-alkenes can serve as anionic olefin equivalent ligands in transition metal chemistry. A chelate ligand of this type is described and used for metal coordination. Deprotonation of the Mes
P(CH
)
B(C
F
)
frustrated Lewis pair in the α-CH[B] position gave the methylene-bridged phosphane/borata-alkene anion. It reacted with the [Rh(nbd)Cl] or [Rh(CO)
Cl] dimers to give the respective neutral chelate [P/C[double bond, length as m-dash]B][Rh] complexes. The reaction of the [P/C[double bond, length as m-dash]B]
anion with [Ir(cod)Cl]
proceeded similarly, only that the complex underwent a subsequent oxidative addition reaction at the mesityl substituent. Both the resulting Ir(iii)hydride complex
and the P/borata-alkene Rh system
were used as hydrogenation catalysts. The [P/C[double bond, length as m-dash]B(C
F
)
]Rh(nbd) complex
served as a catalyst for arylacetylene polymerization.