TY - JOUR
T1 - Carbon-free sandwich compounds based on arsenic and antimony with icosahedral metal cores
AU - Yue, Xu Hui
AU - Chen, Wei Xing
AU - Yang, Tao
AU - Muñoz-Castro, Alvaro
AU - Frenking, Gernot
AU - Sun, Zhong Ming
N1 - Funding Information:
This work was supported by the National Natural Science Foundation of China (92161102, 21971118 and 22003048) and the Natural Science Foundation of Tianjin City (numbers 21JCZXJC00140 and 20JCYBJC01560) to Z.-M.S. Z.-M.S. thanks the 111 project (B18030) from China (MOE). A.M.C. thanks ANID for regular grant 1221676.
Funding Information:
This work was supported by the National Natural Science Foundation of China (92161102, 21971118 and 22003048) and the Natural Science Foundation of Tianjin City (numbers 21JCZXJC00140 and 20JCYBJC01560) to Z.-M.S. Z.-M.S. thanks the 111 project (B18030) from China (MOE). A.M.C. thanks ANID for regular grant 1221676.
Publisher Copyright:
© 2023, The Author(s), under exclusive licence to Springer Nature Limited.
PY - 2023/5
Y1 - 2023/5
N2 - Traditionally, a metallocene complex comprises a metal centre sandwiched between two aromatic organic ligands and such complexes have been extensively investigated. Carbon-free analogues of metallocene with homoleptic As5 or Sb5 ligands, however, have remained experimentally elusive, especially analogues of higher nuclearity. Here we report the synthesis and characterization of sandwich-type clusters [Pn@M12Pn10(Pn5)2]4–/5– (Pn = As, Sb; M = Co, Fe), where the endohedral icosahedral cluster [Pn@M12] can be regarded as a spherical-like three-dimensional coordination centre surrounded by a Pn10 ring and two Pn5 pentagonal caps. Quantum chemical calculations reveal that the [Pn@M12] has orbitals that mimic 1S, 1P and 1D electronic shells, which can interact with the outer (Pn5)2 ring layer. These interactions occur because the frontier orbitals are dominated by the (n − 1)d block orbitals of the metal atoms. The π 1-As5 orbitals interact with 1S and part of the 1P shell of the central core, while the π 2- and π 3-As5 orbitals interact with the symmetry-allowed part of the 1P and 1D shells. The characteristics of this orbital interaction are analogous to those of mononuclear metallocenes. [Figure not available: see fulltext.]
AB - Traditionally, a metallocene complex comprises a metal centre sandwiched between two aromatic organic ligands and such complexes have been extensively investigated. Carbon-free analogues of metallocene with homoleptic As5 or Sb5 ligands, however, have remained experimentally elusive, especially analogues of higher nuclearity. Here we report the synthesis and characterization of sandwich-type clusters [Pn@M12Pn10(Pn5)2]4–/5– (Pn = As, Sb; M = Co, Fe), where the endohedral icosahedral cluster [Pn@M12] can be regarded as a spherical-like three-dimensional coordination centre surrounded by a Pn10 ring and two Pn5 pentagonal caps. Quantum chemical calculations reveal that the [Pn@M12] has orbitals that mimic 1S, 1P and 1D electronic shells, which can interact with the outer (Pn5)2 ring layer. These interactions occur because the frontier orbitals are dominated by the (n − 1)d block orbitals of the metal atoms. The π 1-As5 orbitals interact with 1S and part of the 1P shell of the central core, while the π 2- and π 3-As5 orbitals interact with the symmetry-allowed part of the 1P and 1D shells. The characteristics of this orbital interaction are analogous to those of mononuclear metallocenes. [Figure not available: see fulltext.]
UR - http://www.scopus.com/inward/record.url?scp=85170052962&partnerID=8YFLogxK
U2 - 10.1038/s44160-023-00247-0
DO - 10.1038/s44160-023-00247-0
M3 - Article
AN - SCOPUS:85170052962
SN - 2731-0582
VL - 2
SP - 423
EP - 429
JO - Nature Synthesis
JF - Nature Synthesis
IS - 5
ER -