TY - JOUR
T1 - Silicon–silicon π single bond
AU - Kyushin, Soichiro
AU - Kurosaki, Yoshikuni
AU - Otsuka, Kyohei
AU - Imai, Haruna
AU - Ishida, Shintaro
AU - Kyomen, Toru
AU - Hanaya, Minoru
AU - Matsumoto, Hideyuki
N1 - Funding Information:
This work was supported in part by Grants-in-Aid for Scientific Research (Numbers 18655011 and 19350018) from the Japan Society for the Promotion of Science.
Publisher Copyright:
© 2020, The Author(s).
PY - 2020/12/1
Y1 - 2020/12/1
N2 - A carbon–carbon double bond consists of a σ bond and a π bond. Recently, the concept of a π single bond, where a π bond is not accompanied by a σ bond, has been proposed in diradicals containing carbon and heteroatom radical centers. Here we report a closed-shell compound having a silicon–silicon π single bond. 1,2,2,3,4,4-Hexa-tert-butylbicyclo[1.1.0]tetrasilane has a silicon−silicon π single bond between the bridgehead silicon atoms. The X-ray crystallographic analysis shows that the silicon−silicon π single bond (2.853(1) Å) is far longer than the longest silicon−silicon bond so far reported. In spite of this unusually long bond length, the electrons of the 3p orbitals are paired, which is confirmed by measurement of electron paramagnetic resonance, and magnetic susceptibility and natural bond orbital analysis. The properties of the silicon−silicon π single bond are studied by UV/Vis and 29Si NMR spectroscopy, and theoretical calculations.
AB - A carbon–carbon double bond consists of a σ bond and a π bond. Recently, the concept of a π single bond, where a π bond is not accompanied by a σ bond, has been proposed in diradicals containing carbon and heteroatom radical centers. Here we report a closed-shell compound having a silicon–silicon π single bond. 1,2,2,3,4,4-Hexa-tert-butylbicyclo[1.1.0]tetrasilane has a silicon−silicon π single bond between the bridgehead silicon atoms. The X-ray crystallographic analysis shows that the silicon−silicon π single bond (2.853(1) Å) is far longer than the longest silicon−silicon bond so far reported. In spite of this unusually long bond length, the electrons of the 3p orbitals are paired, which is confirmed by measurement of electron paramagnetic resonance, and magnetic susceptibility and natural bond orbital analysis. The properties of the silicon−silicon π single bond are studied by UV/Vis and 29Si NMR spectroscopy, and theoretical calculations.
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U2 - 10.1038/s41467-020-17815-z
DO - 10.1038/s41467-020-17815-z
M3 - Article
C2 - 32782244
AN - SCOPUS:85089359858
SN - 2041-1723
VL - 11
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 4009
ER -