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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Group 8 metallocenes as single-source precursors for the synthesis of light-element-stabilized FCC phases under
Ken Niwa1,2, Kenta Nakashima2, Yusuke Kimura2
1Research Center for Crystalline Materials Engineering, Faculty of Engineering, Nagoya University, Nagoya, Japan.
Abstract:
Metallocenes are promising single-source precursors for the synthesis of transition-metal carbides and hydrides due to their atomic-scale mixing of metal, carbon, and hydrogen. In this study, we investigated the high-pressure and high-temperature (HP-HT) behavior of group 8 metallocenes, ferrocene [Fe(C5H5)2] and ruthenocene [Ru(C5H5)2], at pressures up to 68 GPa using a laser-heated diamond anvil cell. Optical and Raman spectroscopic observations revealed that both complexes undergo a transition to an opaque state above ~20 GPa, enabling efficient laser coupling. In situ synchrotron X-ray diffraction measurements demonstrated that HP-HT treatment of ferrocene and ruthenocene above 30 GPa yielded the formation of the face-centered cubic phase, which indicates that the decomposition of metallocenes under extreme conditions facilitates the stabilization of exotic, light-element-incorporated metallic phases. Our findings highlight the potential of organometallic precursors in exploring the structural diversity of metal-light element systems under ultrahigh pressures.
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