Open-Shell Germylene Stabilized by a Phenalenyl-Based Ligand

Takuya Kodama; Kenta Uchida; Chihiro Nakasuji; Ryohei Kishi; Yasutaka Kitagawa; Mamoru Tobisu

doi:10.1021/acs.inorgchem.3c00583

Open-Shell Germylene Stabilized by a Phenalenyl-Based Ligand

Inorg Chem. 2023 May 22;62(20):7861-7867. doi: 10.1021/acs.inorgchem.3c00583. Epub 2023 May 10.

Authors

Takuya Kodama^{1

2}, Kenta Uchida¹, Chihiro Nakasuji³, Ryohei Kishi^{2

3

4}, Yasutaka Kitagawa^{2

3

4

5}, Mamoru Tobisu^{1

2}

Affiliations

¹ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 561-0871, Japan.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan.
³ Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 Japan.
⁴ Center for Quantum Information and Quantum Biology (QIQB), Institute for Open and Transdisciplinary Research Initiatives, Osaka University, Toyonaka, Osaka 560-8531, Japan.
⁵ Spintronics Research Network Division, Institute for Open and Transdisciplinary Research Initiatives (SRN-OTRI), Toyonaka, Osaka 560-8531, Japan.

PMID: 37163696
DOI: 10.1021/acs.inorgchem.3c00583

Abstract

An open-shell germylene 1 stabilized by a phenalenyl-based bidentate ligand was synthesized and characterized. Because of the high thermal stability originating from spin delocalization over the phenalenyl moiety, it was possible to isolate compound 1 in crystalline form by sublimation at ca. 300 °C. Electron spin resonance (ESR) spectra, crystallographic analysis, theoretical calculations, and reactivities with carbon radicals suggest that the spin of 1 is distributed on the phenalenyl moiety, while 1 reacted with C₂Cl₆, PhSSPh, and p-benzoquinone at the germanium center to form Ge-E (E = Cl, S, O) bonds. Furthermore, compound 1 is featured by its reactivity as a "formal germylyne", which allows for the formation of three new σ-bonds or one σ-bond with metal complexation on the germanium center.