Bimetallic nickel-lutetium complexes: tuning the properties and catalytic hydrogenation activity of the Ni site by varying the Lu coordination environment

Bianca L. Ramirez, Prachi Sharma, Reed J. Eisenhart, Laura Gagliardi, Connie C. Lu

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We present three heterobimetallic complexes containing an isostructural nickel center and a lutetium ion in varying coordination environments. The bidentate iPr 2PCH 2NHPh and nonadentate ( iPr 2PCH 2NHAr) 3tacn ligands were used to prepare the Lu metalloligands, Lu( iPr 2PCH 2NPh) 3 ( 1) and Lu{( iPr 2PCH 2NAr) 3tacn} ( 2), respectively. Reaction of Ni(COD) 2 (where COD is 1,5-cyclooctadiene) and 1 afforded NiLu( iPr 2PCH 2NPh) 3 ( 3), with a Lu coordination number (CN) of 4 and a Ni-Lu distance, d(Ni-Lu), of 2.4644(2) Å. Complex 3 can further bind THF to form 3-THF, increasing both the Lu CN to 5 and d(Ni-Lu) to 2.5989(4) Å. On the other hand, incorporation of Ni(0) into 2 provides NiLu{( iPr 2PCH 2NAr) 3tacn} ( 4), in which the Lu coordination environment is more saturated (CN = 6), and the d(Ni-Lu) is substantially elongated at 2.9771(5) Å. Cyclic voltammetry of the three Ni-Lu complexes shows an overall ∼410 mV shift in the Ni(0/I) redox couple, suggesting tunability of the Ni electronics across the series. Computational studies reveal polarized bonding interactions between the Ni 3d z 2 (major) and the Lu 5d z 2 (minor) orbitals, where the percentage of Lu character increases in the order: 4 (6.0% Lu 5d z 2 ) < 3-THF (8.5%) < 3 (9.3%). All three Ni-Lu complexes bind H 2 at low temperatures (-30 to -80 °C) and are competent catalysts for styrene hydrogenation. Complex 3 outperforms 4 with a four-fold faster rate. Additionally, adding increasing THF equivalents to 3, which would favor build-up of 3-THF, decreases the rate. We propose that altering the coordination sphere of the Lu support can influence the resulting properties and catalytic activity of the active Ni(0) metal center.

Original languageEnglish (US)
Pages (from-to)3375-3384
Number of pages10
JournalChemical Science
Issue number11
StatePublished - 2019

Bibliographical note

Funding Information:
The authors thank Dr Laura J. Clouston and Dr Dale R. Pahls for preliminary results and helpful discussions. BLR 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) for support. The computational work was supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, of the U.S. Department of Energy under Grant USDOE/ DESC002183. 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.

Publisher Copyright:
© The Royal Society of Chemistry.

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