Synthesis, Characterization, and Reactivity of a High-Spin Iron(II) Hydrido Complex Supported by a PNP Pincer Ligand and Its Application as a Homogenous Catalyst for the Hydrogenation of Alkenes

Inorganic Chemistry
Jonas C OttLutz H Gade

Abstract

This study focused on the synthesis and characterization of a range of low-valent, high-spin iron(II) complexes supported by a carbazole-based PNP pincer-type ligand. The addition of the lithiated ligand (PNP)Li to FeCl2(THF)1.5yielded the chlorido complex (PNP)FeCl (1), which could be readily converted to the four-coordinate iron(II) alkyl complexes (PNP)FeR [R = CH2SiMe3(3a), Me (3b), CH2Ph (3c)]. These iron(II) complexes were fully characterized by X-ray analysis and a comprehensive, density-functional-theory-assisted study with complete assignment of their paramagnetic1H and13C NMR spectra. Treatment of 1 with KHBEt3or the addition of molecular hydrogen to (PNP)FeR afforded a high-spin iron(II) PNP hydrido complex, which was identified as the dimer [(PNP)Fe(μ-H)]2(4) with two bridging hydrido ligands between the iron centers. Exposing complexes 1 and 4 to carbon monoxide led to the corresponding six-coordinate, diamagnetic complexes (PNP)Fe(CO)2Cl (2) and (PNP)Fe(CO)2H (5), of which 2 was present as cis/trans isomers. Furthermore, 4 was found to be an active catalyst for the hydrogenation of alkenes.

References

Dec 18, 2003·Journal of the American Chemical Society·Jeremy M SmithPatrick L Holland
Dec 9, 2004·Chemical Reviews·Carsten BolmLorenzo Zani
Apr 28, 2005·Journal of the American Chemical Society·Robert Y IgarashiBrian M Hoffman
Jan 19, 2006·Journal of the American Chemical Society·Jeremy M SmithPatrick L Holland
Dec 1, 1976·Proceedings of the National Academy of Sciences of the United States of America·L Pauling
May 1, 2007·Angewandte Chemie·Gérard CahiezAlban Moyeux
Jul 31, 2007·Journal of the American Chemical Society·Takuji Hatakeyama, Masaharu Nakamura
Sep 7, 2007·Accounts of Chemical Research·Nicholas B JohnsonJames A Ramsden
May 1, 2008·Journal of the American Chemical Society·Ying YuPatrick L Holland
Jul 24, 2008·Accounts of Chemical Research·Patrick L Holland
Feb 13, 2010·Science·Paul J Chirik, Karl Wieghardt
Nov 6, 2010·Chemical Reviews·Chang-Liang SunZhang-Jie Shi
Aug 1, 2009·Nature Chemistry·Carsten Bolm
Mar 26, 2011·Chemical Communications : Chem Comm·Kathrin JungeMatthias Beller
Mar 7, 2013·Chemical Reviews·Kovuru Gopalaiah
Sep 4, 2013·Organometallics·Henry FongJonas C Peters
Jun 1, 2014·Journal of the American Chemical Society·Sumit ChakrabortyWilliam D Jones
Mar 10, 2015·Chemical Reviews·Ingmar Bauer, Hans-Joachim Knölker
Jul 28, 2015·Accounts of Chemical Research·Eric McNeill, Tobias Ritter
Mar 31, 2016·Journal of the American Chemical Society·Trevor J Del CastilloJonas C Peters
Apr 6, 2017·Chemical Reviews·Rui ShangEiichi Nakamura
Dec 22, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Junichi HiguchiYoshiaki Nishibayashi

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Citations

Jul 18, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Ryan R LangeslayMassimiliano Delferro
Jan 18, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Latchupatula RadhakrishnaMaravanji S Balakrishna

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