A combination of four-electron donors, such as alkynes, with strongly donating and strong-field scorpionate ligands is appropriate to create pseudotetrahedral rhodium(I) environments, as found in [Rh(PhBP3 )(HCCPh)], which promotes HC bond activation and CC coupling reactions under very smooth conditions.
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Pseudo-tetrahedral Rhodium and Iridium Complexes: Catalytic Synthesis of E-Enynes.
Chemistry
November 2018
Departamento de Química Inorgánica, Instituto de Síntesis QuímicayCatálisis Homogénea-ISQCH, CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009, Zaragoza, Spain.
The reactions of the rhodium(I) and iridium(I) complexes [M(PhBP )(C H )(NCMe)] (PhBP =PhB(CH PPh ) ) with alkynes have resulted in the synthesis of a new family of pseudo-tetrahedral complexes, [M(PhBP )(RC≡CR')] (M=Rh, Ir), which contain the alkyne as a four-electron donor. The reactions of these unusual compounds with two-electron donors (L=PMe , CNtBu) produced a change in the "donicity" of the alkyne from a 4e to a 2e donor to give five-coordinate complexes. These were the final products with the iridium complexes, whereas further reactions took place with the rhodium complexes.
View Article and Find Full Text PDFTerminal imido rhodium complexes.
Angew Chem Int Ed Engl
May 2014
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain).
Compounds of the late transition metals with M=X multiple bonds (X=CR2, NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but with noticeable gaps in the second- and third-row elements. For example, there are no isolated examples of terminal imido rhodium complexes known to date. Described herein is the isolation, characterization, and some preliminary reactivity studies of the first rhodium complexes [Rh(PhBP3)(NR)] (PhBP3=PhB{CH2PPh2}3) with a multiple and terminal Rh=N bond.
View Article and Find Full Text PDFPseudotetrahedral rhodium(I) complexes.
Chemistry
March 2014
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009-Zaragoza (Spain).
A combination of four-electron donors, such as alkynes, with strongly donating and strong-field scorpionate ligands is appropriate to create pseudotetrahedral rhodium(I) environments, as found in [Rh(PhBP3 )(HCCPh)], which promotes HC bond activation and CC coupling reactions under very smooth conditions.
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