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Altering Charges on Heterobimetallic Transition‐Metal Carbonyl Clusters
Author(s) -
Unkrig Wiebke,
Kloiber Konstantin,
Butschke Burkhard,
Kratzert Daniel,
Krossing Ingo
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002339
Subject(s) - superatom , crystallography , homoleptic , chemistry , trigonal bipyramidal molecular geometry , cluster (spacecraft) , bipyramid , octahedron , transition metal , trigonal prismatic molecular geometry , molecule , stoichiometry , ion , metal , trimer , crystal structure , density functional theory , computational chemistry , biochemistry , organic chemistry , catalysis , programming language , dimer , computer science
The homoleptic group 5 carbonylates [M(CO) 6 ] − (M=Nb, Ta) serve as ligands in carbonyl‐terminated heterobimetallic Ag m M n clusters containing 3 to 11 metal atoms. Based on our serendipitous [Ag 6 {Nb(CO) 6 } 4 ] 2+ ( 4 a 2+ ) precedent, we established access to such Ag m M n clusters of the composition [Ag m {M(CO) 6 } n ] x (M=Nb, Ta; m =1, 2, 6; n =2, 3, 4, 5; x= 1−, 1+, 2+). Salts of those molecular cluster ions were synthesized by the reaction of [NEt 4 ][M(CO) 6 ] and Ag[Al(OR F ) 4 ] (R F =C(CF 3 ) 3 ) in the correct stoichiometry in 1,2,3,4‐tetrafluorobenzene at −35 °C. The solid‐state structures were determined by single‐crystal X‐ray diffraction methods and, owing to the thermal instability of the clusters, a limited scope of spectroscopic methods. In addition, DFT‐based AIM calculations were performed to provide an understanding of the bonding within these clusters. Apparently, the clusters 3 + ( m =6, n =5) and 4 2+ ( m =6, n =4) are superatom complexes with trigonal‐prismatic or octahedral Ag 6 superatom cores. The [M(CO) 6 ] − ions then bind through three CO units as tridentate chelate ligands to the superatom core, giving overall structures related to tetrahedral AX 4 ( 4 2+ ) or trigonal bipyramidal AX 5 molecules ( 3 + ).