Boryl-functionalized σ-alkynyl and vinylidene rhodium complexes: synthesis and electronic properties.
The synthesis, reactivity, and properties of boryl-functionalized σ-alkynyl and vinylidene rhodium complexes such as trans-[RhCl(=C=CHBMes2)(PiPr3)2] and trans-[Rh(C≡CBMes2)(IMe)(PiPr3)2] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ-alkynyl complexes in solution. The complex trans-[Rh(C≡CBMes2)(IMe)(PiPr3)2] (IMe=1,3-dimethylimidazol-2-ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans-[Rh(C≡CBMes2)(IMe)(PiPr3)2].
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany). h.braunschweig@mail.uni-wuerzburg.de.
Holger
H
Braunschweig
Christopher K L
CK
Brown
Rian D
RD
Dewhurst
J Oscar C
JO
Jimenez-Halla
Thomas
T
Kramer
Ivo
I
Krummenacher
Bernd
B
Pfaffinger
alkynyl ligands; boron; rhodium; solvatochromism; vinylidene ligands