Multiple‐Bonding and Lability: Study of an Anionic Vanadium Alumanyl
Abstract
ABSTRACT An anionic vanadium alumanyl complex is prepared by a reaction of neutral vanadocene and an alumanyl anion. Single‐crystal XRD revealed a significantly contracted V–Al bond relative to that of the neutral congener. Theoretical calculations using IBO and QTAIM analysis attributed this contraction to enhanced multiple‐bonding character based on the d‐p π‐backdonation from V to Al. Magnetic data confirms the S = 1/2 spin state of this anion, with EPR spectroscopy displaying relatively strong coupling between the V‐centered unpaired electron and the 27 Al nucleus. Furthermore, V K ‐edge XANES and XPS data revealed the oxidation states of the V and Al centers, highlighting the reduced nature of both metal centers. Reactivity studies revealed the dissociation of the anionic alumanyl ligand from the V center even in the presence of the multiple V─Al bond character, in stark contrast to the reactivity of the neutral analogue, as supported by a DFT‐based mechanistic study.
Article Details
Authors (8)
Pavel Zatsepin
Department of Chemistry School of Science Institute of Science Tokyo Meguro‐ku Tokyo Japan
Chaoqi Chen
Department of Chemistry Graduate School of Science Nagoya University, Furo‐cho, Chikusa‐ku Nagoya Aichi Japan
Takumi Moriyama
Department of Chemistry Graduate School of Science Nagoya University, Furo‐cho, Chikusa‐ku Nagoya Aichi Japan
Satoshi Muratsugu
Department of Chemistry Graduate School of Science Nagoya University, Furo‐cho, Chikusa‐ku Nagoya Aichi Japan
Mizuki Tada
Department of Chemistry, Graduate School of Science, Research Center for Materials Science, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Nagoya, Aichi 464-8602, Japan
Ka Lok Chan
Department of Chemistry The Hong Kong University of Science and Technology, Clear Water Bay Kowloon Hong Kong
Zhenyang Lin
Makoto Yamashita
Department of Chemistry School of Science Institute of Science Tokyo Meguro‐ku Tokyo Japan