Rare-Earth Supported Nickel Catalysts for Alkyne Semihydrogenation: Chemo- And Regioselectivity Impacted by the Lewis Acidity and Size of the Support

Bianca L. Ramirez, Connie C. Lu

Research output: Contribution to journalArticlepeer-review

90 Scopus citations


Bimetallic catalysts of nickel(0) with a trivalent rare-earth ion or Ga(III), NiML3 (where L is [iPr2PCH2NPh]-, and M is Sc, Y, La, Lu, or Ga), were investigated for the selective hydrogenation of diphenylacetylene (DPA) to (E)-stilbene. Each bimetallic complex features a relatively short Ni-M bond length, ranging from 2.3395(8) Å (Ni-Ga) to 2.5732(4) Å (Ni-La). The anodic peak potentials of the NiML3 complexes vary from -0.48 V to -1.23 V, where the potentials are negatively correlated with the Lewis acidity of the M(III) ion. Three catalysts, Ni-Y, Ni-Lu, and Ni-Ga, showed nearly quantitative conversions in the semihydrogenation of DPA, with NiYL3 giving the highest selectivity for (E)-stilbene. Initial rate studies were performed on the two tandem catalytic reactions: DPA hydrogenation and (Z)-stilbene isomerization. The catalytic activity in DPA hydrogenation follows the order Ni-Ga > Ni-La > Ni-Y > Ni-Lu > Ni-Sc. The ranking of catalysts by (Z)-stilbene isomerization initial rates is Ni-Ga ≫ Ni-Sc > Ni-Lu > Ni-Y > Ni-La. In operando 31P and 1H NMR studies revealed that in the presence of DPA, the Ni bimetallic complexes supported by Y, Lu, and La form the Ni(η2-alkyne) intermediate, (η2-PhCCPh)Ni(iPr2PCH2NPh)2M(κ2-iPr2PCH2NPh). In contrast, the Ni-Ga resting state is the Ni(η2-H2) species, and Ni-Sc showed no detectable binding of either substrate. Hence, the mechanism of Ni-catalyzed diphenylacetylene semihydrogenation adheres to two different kinetics: an autotandem pathway (Ni-Ga, Ni-Sc) versus temporally separated tandem reactions (Ni-Y, Ni-Lu, Ni-La). Collectively, the experimental results demonstrate that modulating a base-metal center via a covalently appended Lewis acidic support is viable for promoting selective alkyne semihydrogenation.

Original languageEnglish (US)
Pages (from-to)5396-5407
Number of pages12
JournalJournal of the American Chemical Society
Issue number11
StatePublished - Mar 18 2020

Bibliographical note

Funding Information:
B.L.R. is grateful to 3M for a research fellowship. The experimental work was supported by the American Chemical Society Petroleum Research Fund (57192-ND3). C.C.L. acknowledges the National Science Foundation (CHE-1665010 and CHE-1954751) for support. X-ray diffraction experiments were performed using a crystal diffractometer acquired through an NSF-MRI award (CHE-1229400) in the X-ray laboratory supervised by Dr. Victor G. Young, Jr. B.L.R. thanks Dr. Victor G. Young, Jr. for assistance with X-ray crystallography and Dr. Letitia J. Yao for assistance with NMR spectroscopy.

Publisher Copyright:
Copyright © 2020 American Chemical Society.


Dive into the research topics of 'Rare-Earth Supported Nickel Catalysts for Alkyne Semihydrogenation: Chemo- And Regioselectivity Impacted by the Lewis Acidity and Size of the Support'. Together they form a unique fingerprint.

Cite this