Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

Cory J. Windorff; Cristian Celis-Barros; Joseph M. Sperling; Noah C. McKinnon; Thomas E. Albrecht-Schmitt

doi:10.1039/c9sc05268b

Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

Cory J. Windorff, Cristian Celis-Barros, Joseph M. Sperling, Noah C. McKinnon, Thomas E. Albrecht-Schmitt

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

24 Scopus citations

Abstract

The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), mer-AmBr₃(OPcy₃)₃, has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo trans ligands display significantly shorter bonds than the cis or hetero trans ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, i.e. americium shows the most covalent interactions compared to lanthanides. However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ∼ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes.

Original language	English
Pages (from-to)	2770-2782
Number of pages	13
Journal	Chemical Science
Volume	11
Issue number	10
DOIs	https://doi.org/10.1039/c9sc05268b
State	Published - Mar 14 2020
Externally published	Yes

Funding

We thank the support of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry program under Award Number DE-FG02-13ER16414. The 243Am used in this research were supplied by the U.S. Department of Energy Isotope Program, managed by the Office of Science for Nuclear Physics. We thank Dr Benjamin W. Stein and Dr Conrad A. P. Goodwin of Los Alamos National Laboratory for helpful discussions. We are grateful to Dr Ion Ghiviriga, Prof. Adam Veige, and Dr Banghao Chen for their assistance with the NMR experiments as well as Dr Xinsong Lin for his assistance with the DART-MS. We thank Mr Jason Johnson and Ms Ashley Gray of Florida State University for radiological assistance.

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-FG02-13ER16414

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10.1039/c9sc05268b

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title = "Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes",

abstract = "The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), mer-AmBr3(OPcy3)3, has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo trans ligands display significantly shorter bonds than the cis or hetero trans ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, i.e. americium shows the most covalent interactions compared to lanthanides. However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ∼ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes.",

author = "Windorff, {Cory J.} and Cristian Celis-Barros and Sperling, {Joseph M.} and McKinnon, {Noah C.} and Albrecht-Schmitt, {Thomas E.}",

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T1 - Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

AU - Windorff, Cory J.

AU - Celis-Barros, Cristian

AU - Sperling, Joseph M.

AU - McKinnon, Noah C.

AU - Albrecht-Schmitt, Thomas E.

PY - 2020/3/14

Y1 - 2020/3/14

N2 - The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), mer-AmBr3(OPcy3)3, has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo trans ligands display significantly shorter bonds than the cis or hetero trans ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, i.e. americium shows the most covalent interactions compared to lanthanides. However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ∼ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes.

AB - The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), mer-AmBr3(OPcy3)3, has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo trans ligands display significantly shorter bonds than the cis or hetero trans ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, i.e. americium shows the most covalent interactions compared to lanthanides. However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ∼ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes.

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VL - 11

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JO - Chemical Science

JF - Chemical Science

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Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

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