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On the Nature of Actinide– and Lanthanide–Metal Bonds in Heterobimetallic Compounds
Author(s) -
Vlaisavljevich Bess,
Miró Pere,
Cramer Christopher J.,
Gagliardi Laura,
Infante Ivan,
Liddle Stephen T.
Publication year - 2011
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.201100774
Subject(s) - lanthanide , chemistry , actinide , metal , crystallography , density functional theory , quantum chemical , ionic bonding , complete active space , computational chemistry , molecule , inorganic chemistry , stereochemistry , ion , organic chemistry , basis set
Abstract Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f‐block and other elements were examined by quantum chemical methods: [(η 5 ‐C 5 H 5 ) 2 (THF)LuRu(η 5 ‐C 5 H 5 ) (CO) 2 ], [(η 5 ‐C 5 Me 5 ) 2 (I)ThRu(η 5 ‐C 5 H 5 ) (CO) 2 ], [(η 5 ‐C 5 H 5 ) 2 YRe(η 5 ‐C 5 H 5 ) 2 ], [{N(CH 2 CH 2 NSiMe 3 ) 3 }URe(η 5 ‐C 5 H 5 ) 2 ], [Y{Ga(NArCh) 2 }{C(PPh 2 NSiH 3 ) 2 }(CH 3 OCH 3 ) 2 ], [{N(CH 2 CH 2 NSiMe 3 ) 3 }U{Ga(NArCH) 2 }(THF)], [(η 5 ‐C 5 H 5 ) 3 UGa(η 5 ‐C 5 Me 5 )], [Yb(η 5 ‐C 5 H 5 ){Si(SiMe 3 ) 3 (THF) 2 }], [(η 5 ‐C 5 H 5 ) 3 U(SnPh 3 )], [(η 5 ‐C 5 H 5 ) 3 U(SiPh 3 )], and (Ph[Me]N) 3 USi(SiMe 3 ) 3 . Geometries in good agreement with experiment were obtained at the density functional level of theory. The multiconfigurational complete active space self‐consistent field method (CASSCF) and subsequent corrections with second order perturbation theory (CASPT2) were applied to further understand the electronic structure of the lanthanide/actinide–metal (or metal–metalloid) bonds. Fragment calculations and energy‐decomposition analyses were also performed and indicate that charge transfer occurs from one supported metal fragment to the other, while the bonding itself is always dominated by ionic character.