Distinct electronic structures and bonding interactions in inverse-sandwich samarium and ytterbium biphenyl complexes.

Autor:	Xiao Y; Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Material Chemistry and Application, College of Chemistry and Molecular Engineering, Peking University Beijing 100871 P. R. China wlhuang@pku.edu.cn., Zhao XK; Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University Beijing 100084 P. R. China hshu@mail.tsinghua.edu.cn., Wu T; Chemical Sciences and Engineering Division, Argonne National Laboratory Argonne Illinois 60439 USA., Miller JT; Chemical Sciences and Engineering Division, Argonne National Laboratory Argonne Illinois 60439 USA., Hu HS; Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University Beijing 100084 P. R. China hshu@mail.tsinghua.edu.cn., Li J; Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University Beijing 100084 P. R. China hshu@mail.tsinghua.edu.cn., Huang W; Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Material Chemistry and Application, College of Chemistry and Molecular Engineering, Peking University Beijing 100871 P. R. China wlhuang@pku.edu.cn., Diaconescu PL; Department of Chemistry and Biochemistry, University of California Los Angeles California 90095 USA pld@chem.ucla.edu.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2020 Oct 29; Vol. 12 (1), pp. 227-238. Date of Electronic Publication: 2020 Oct 29.
DOI:	10.1039/d0sc03555f
Abstrakt:	Inverse-sandwich samarium and ytterbium biphenyl complexes were synthesized by the reduction of their trivalent halide precursors with potassium graphite in the presence of biphenyl. While the samarium complex had a similar structure as previously reported rare earth metal biphenyl complexes, with the two samarium ions bound to the same phenyl ring, the ytterbium counterpart adopted a different structure, with the two ytterbium ions bound to different phenyl rings. Upon the addition of crown ether to encapsulate the potassium ions, the inverse-sandwich samarium biphenyl structure remained intact; however, the ytterbium biphenyl structure fell apart with the concomitant formation of a divalent ytterbium crown ether complex and potassium biphenylide. Spectroscopic and computational studies were performed to gain insight into the electronic structures and bonding interactions of these samarium and ytterbium biphenyl complexes. While the ytterbium ions were found to be divalent with a 4f 14 electron configuration and form a primarily ionic bonding interaction with biphenyl dianion, the samarium ions were in the trivalent state with a 4f 5 electron configuration and mainly utilized the 5d orbitals to form a δ-type bonding interaction with the π* orbitals of the biphenyl tetraanion, showing covalent character. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
Externí odkaz:	Zobrazit plný text záznamu