@article{ce949e271bee401f8971d03c3eaa1fe7,
title = "Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions",
abstract = "The discovery of ferrocene nearly 70 years ago marked the genesis of metallocene chemistry. Although the ferrocenium cation was discovered soon afterwards, a derivatized ferrocenium dication was only isolated in 2016 and the monoanion of ferrocene has only been observed in low-temperature electrochemical studies. Here we report the isolation of a derivatized ferrocene anion in the solid state as part of an isostructural family of 3d metallocenates, which consist of anionic complexes of a metal centre (manganese, iron or cobalt) sandwiched between two bulky Cp ttt ligands (where Cp ttt is {1,2,4-C 5H 2 tBu 3}). These thermally and air-sensitive complexes decompose rapidly above −30 °C; however, we were able to characterize all metallocenates by a wide range of physical techniques and ab initio calculations. These data have allowed us to map the electronic structures of this metallocenate family, including an unexpected high-spin S = 3/2 ground state for the 19e − derivatized ferrocene anion. [Figure not available: see fulltext.] ",
author = "Conrad Goodwin and Marcus Giansiracusa and Samuel Greer and Hannah Nicholas and Peter Evans and Michele Vonci and Stephen Hill and Nicholas Chilton and David Mills",
note = "Funding Information: We acknowledge funding from the Engineering and Physical Sciences Research Council (Doctoral Prize Fellowship to C.A.P.G., EP/N007034/1 for M.V., EP/R002605X/1 for P.E., studentship for H.M.N. and EP/K039547/1 for a single-crystal X-ray diffractometer), the Royal Society (University Research Fellowship to N.F.C.), European Research Council CoG-816268 (D.P.M. and M.J.G.) and StG-851504 (N.F.C.) and the University of Manchester (Presidential Doctoral Prize to M.J.G.). C.A.P.G. and S.M.G. thank the Laboratory Directed Research and Development (LDRD) programme at Los Alamos National Laboratory (an affirmative action/equal opportunity employer, managed by Triad National Security, LLC, for the NNSA of the US Department of Energy) (contract no. 89233218CNA000001) for a distinguished J. Robert Oppenheimer Postdoctoral Fellowship and Directors Fellowship, respectively. S.H. acknowledges support from the National Science Foundation (DMR-1610226). We thank the EPSRC UK National Electron Paramagnetic Resonance Service for access to the EPR Facility, and the University of Manchester for access to the Computational Shared Facility. A portion of this work was performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative agreement no. DMR-1644779 and the State of Florida. We also thank F. Ortu for assistance with the collection of Raman spectra. This project has received funding from the European Research Council (ERC) under the European Union{\textquoteright}s Horizon 2020 research and innovation programme (grant agreements nos. 816268 and 851504). Publisher Copyright: {\textcopyright} 2020, The Author(s), under exclusive licence to Springer Nature Limited.",
year = "2020",
month = dec,
day = "14",
doi = "10.1038/s41557-020-00595-w",
language = "English",
volume = "13",
pages = "243--248",
journal = "Nature Chemistry",
issn = "1755-4330",
publisher = "Springer Nature",
number = "3",
}