On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

Bess Vlaisavljevich; Pere Mirõ; Christopher J. Cramer; Laura Gagliardi; Ivan Infante; Stephen T. Liddle

doi:10.1002/chem.201100774

On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

Bess Vlaisavljevich, Pere Mirõ, Christopher J. Cramer, Laura Gagliardi, Ivan Infante, Stephen T. Liddle

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

102 Scopus citations

Abstract

Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(Î·⁵-C₅H ₅)₂(THF)LuRu(Î·⁵-C ₅H₅) (CO)₂], [(Î·⁵- C₅Me₅)₂(I)ThRu(Î·⁵- C₅H₅) (CO)₂], [(Î·⁵- C₅H₅)₂YRe(Î·⁵-C ₅H₅)₂], [{N(CH₂CH ₂NSiMe₃)₃}URe(Î·⁵- C₅H₅)₂], [Y{Ga(NArCh)₂}{C(PPh ₂NSiH₃)₂}(CH₃OCH₃) ₂], [{N(CH₂CH₂NSiMe₃) ₃}U{Ga(NArCH)₂}(THF)], [(Î·⁵- C₅H₅)₃UGa(Î·⁵-C ₅Me₅)], [Yb(Î·⁵-C ₅H₅){Si(SiMe₃)₃(THF)₂}], [(Î·⁵-C₅H₅)₃U(SnPh ₃)], [(Î·⁵-C₅H₅) ₃U(SiPh₃)], and (Ph[Me]N)₃USi(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.

Original language	English (US)
Pages (from-to)	8424-8433
Number of pages	10
Journal	Chemistry - A European Journal
Volume	17
Issue number	30
DOIs	https://doi.org/10.1002/chem.201100774
State	Published - Jul 18 2011

Keywords

actinides
density functional calculations
energy-decomposition analysis
lanthanides
metal-metal bonds

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10.1002/chem.201100774

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@article{46f5cebaf8534c87acdaf16e5c9d6881,

title = "On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds",

abstract = "Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [({\^I}·5-C5H 5)2(THF)LuRu({\^I}·5-C 5H5) (CO)2], [({\^I}·5- C5Me5)2(I)ThRu({\^I}·5- C5H5) (CO)2], [({\^I}·5- C5H5)2YRe({\^I}·5-C 5H5)2], [{N(CH2CH 2NSiMe3)3}URe({\^I}·5- C5H5)2], [Y{Ga(NArCh)2}{C(PPh 2NSiH3)2}(CH3OCH3) 2], [{N(CH2CH2NSiMe3) 3}U{Ga(NArCH)2}(THF)], [({\^I}·5- C5H5)3UGa({\^I}·5-C 5Me5)], [Yb({\^I}·5-C 5H5){Si(SiMe3)3(THF)2}], [({\^I}·5-C5H5)3U(SnPh 3)], [({\^I}·5-C5H5) 3U(SiPh3)], and (Ph[Me]N)3USi(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.",

keywords = "actinides, density functional calculations, energy-decomposition analysis, lanthanides, metal-metal bonds",

author = "Bess Vlaisavljevich and Pere Mir{\~o} and Cramer, {Christopher J.} and Laura Gagliardi and Ivan Infante and Liddle, {Stephen T.}",

year = "2011",

month = jul,

day = "18",

doi = "10.1002/chem.201100774",

language = "English (US)",

volume = "17",

pages = "8424--8433",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "30",

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TY - JOUR

T1 - On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

AU - Vlaisavljevich, Bess

AU - Mirõ, Pere

AU - Cramer, Christopher J.

AU - Gagliardi, Laura

AU - Infante, Ivan

AU - Liddle, Stephen T.

PY - 2011/7/18

Y1 - 2011/7/18

N2 - Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(Î·5-C5H 5)2(THF)LuRu(Î·5-C 5H5) (CO)2], [(Î·5- C5Me5)2(I)ThRu(Î·5- C5H5) (CO)2], [(Î·5- C5H5)2YRe(Î·5-C 5H5)2], [{N(CH2CH 2NSiMe3)3}URe(Î·5- C5H5)2], [Y{Ga(NArCh)2}{C(PPh 2NSiH3)2}(CH3OCH3) 2], [{N(CH2CH2NSiMe3) 3}U{Ga(NArCH)2}(THF)], [(Î·5- C5H5)3UGa(Î·5-C 5Me5)], [Yb(Î·5-C 5H5){Si(SiMe3)3(THF)2}], [(Î·5-C5H5)3U(SnPh 3)], [(Î·5-C5H5) 3U(SiPh3)], and (Ph[Me]N)3USi(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.

AB - Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(Î·5-C5H 5)2(THF)LuRu(Î·5-C 5H5) (CO)2], [(Î·5- C5Me5)2(I)ThRu(Î·5- C5H5) (CO)2], [(Î·5- C5H5)2YRe(Î·5-C 5H5)2], [{N(CH2CH 2NSiMe3)3}URe(Î·5- C5H5)2], [Y{Ga(NArCh)2}{C(PPh 2NSiH3)2}(CH3OCH3) 2], [{N(CH2CH2NSiMe3) 3}U{Ga(NArCH)2}(THF)], [(Î·5- C5H5)3UGa(Î·5-C 5Me5)], [Yb(Î·5-C 5H5){Si(SiMe3)3(THF)2}], [(Î·5-C5H5)3U(SnPh 3)], [(Î·5-C5H5) 3U(SiPh3)], and (Ph[Me]N)3USi(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.

KW - actinides

KW - density functional calculations

KW - energy-decomposition analysis

KW - lanthanides

KW - metal-metal bonds

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SN - 0947-6539

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 30

ER -

On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

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