Stabilization of Pu(IV) in PuBr4(OPCy3)2 and Comparisons with Structurally Similar ThX4(OPR3)2 (R = Cy, Ph) Molecules

Cory J. Windorff; Conrad A. P. Goodwin; Joseph M. Sperling; Thomas E. Albrecht-Schönzart; Zhuanling Bai; William J. Evans; Zachary K.  Huffmann; Renaud   Jeannin; Brian N.  Long; David P. Mills; Todd N. Poe; Joseph W. Ziller

doi:10.1021/acs.inorgchem.3c02575

Stabilization of Pu(IV) in PuBr₄₍OPCy₃)₂ and Comparisons with Structurally Similar ThX4(OPR₃)₂ (R = Cy, Ph) Molecules

Cory J. Windorff
, Conrad A. P. Goodwin
, Joseph M. Sperling
, Thomas E. Albrecht-Schönzart
, Zhuanling Bai
, William J. Evans
, Zachary K. Huffmann
, Renaud Jeannin
, Brian N. Long
, David P. Mills
, Todd N. Poe
, Joseph W. Ziller

Inorganic Chemistry Group

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

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Abstract

The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., "PuBr₃(OPR)₃," instead led to the isolation of the tetravalent trans Pu^IVBr₄(OPCy₃)₂, PuBr/Cy, compound by spontaneous oxidation of Pu^III. Generally, binary Pu^IV halides are unstable in both solution- and solid-state compounds. The donating nature of phosphine oxides has allowed the isolation and characterization of PuBr/Cy by crystallographic, multi-nuclear NMR, solid state and solution phase UV-vis-NIR spectroscopic techniques. The presence of a putative plutonyl(VI) complex formulated as "trans-Pu^VIO₂Br₂(OPCy₃)₂" was also observed spectroscopically and tentatively observed by single-crystal X-ray diffraction as a co-crystal of PuBr/Cy. A series of transThX₄(OPCy₃)₂ (X = Cl, ThCl/Cy; Br, ThBr/Cy; I, ThI/Cy) complexes were synthesized for comparison to PuBr/Cy. The triphenylphosphine oxide, OPPh₃, complexes trans-AnI₄(OPPh₃)₂,
(An = Th, ThI/Ph; U, UI/Ph) were also synthesized for comparison completing the series transUX₄(OPPh₃)₂ (X = Cl, Br, I), UX/Ph. To enable the synthesis of ThI/Cy and ThI/Ph, a new nonaqueous thorium-iodide starting material, ThI4(Et₂O)₂, was synthesized. The synthesis of organic solvent soluble ThI4L₂ (L = Et₂O, OPCy₃, and OPPh₃) are the first examples of crystallographically characterized neutral thorium tetraiodide materials beyond binary ThI4. To show the viability of
ThI4(Et₂O)₂ as a starting material for organothorium chemistry (C₅Me₄H)₃ThI was synthesized and crystallographically characterized.

Original language	English
Journal	Inorganic Chemistry
DOIs	https://doi.org/10.1021/acs.inorgchem.3c02575
Publication status	Published - 24 Oct 2023

Keywords

Plutonium
Actinide
Tetravalent
Octahedral
Phosphine oxide

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10.1021/acs.inorgchem.3c02575

AnX4(OPR3)_R2_CJWAccepted author manuscript, 2.21 MBLicence: CC BY

Cite this

Windorff, C. J., Goodwin, C. A. P., Sperling, J. M., Albrecht-Schönzart, T. E., Bai, Z., Evans, W. J., Huffmann, Z. K., Jeannin, R., Long, B. N., Mills, D. P., Poe, T. N., & Ziller, J. W. (2023). Stabilization of Pu(IV) in PuBr₄₍OPCy₃)₂ and Comparisons with Structurally Similar ThX4(OPR₃)₂ (R = Cy, Ph) Molecules. Inorganic Chemistry . https://doi.org/10.1021/acs.inorgchem.3c02575

@article{df82abf12ccd437199a89090ef98f8e0,

title = "Stabilization of Pu(IV) in PuBr4(OPCy3)2 and Comparisons with Structurally Similar ThX4(OPR3)2 (R = Cy, Ph) Molecules",

abstract = "The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., {"}PuBr3(OPR)3,{"} instead led to the isolation of the tetravalent trans PuIVBr4(OPCy3)2, PuBr/Cy, compound by spontaneous oxidation of PuIII. Generally, binary PuIV halides are unstable in both solution- and solid-state compounds. The donating nature of phosphine oxides has allowed the isolation and characterization of PuBr/Cy by crystallographic, multi-nuclear NMR, solid state and solution phase UV-vis-NIR spectroscopic techniques. The presence of a putative plutonyl(VI) complex formulated as {"}trans-PuVIO2Br2(OPCy3)2{"} was also observed spectroscopically and tentatively observed by single-crystal X-ray diffraction as a co-crystal of PuBr/Cy. A series of transThX4(OPCy3)2 (X = Cl, ThCl/Cy; Br, ThBr/Cy; I, ThI/Cy) complexes were synthesized for comparison to PuBr/Cy. The triphenylphosphine oxide, OPPh3, complexes trans-AnI4(OPPh3)2, (An = Th, ThI/Ph; U, UI/Ph) were also synthesized for comparison completing the series transUX4(OPPh3)2 (X = Cl, Br, I), UX/Ph. To enable the synthesis of ThI/Cy and ThI/Ph, a new nonaqueous thorium-iodide starting material, ThI4(Et2O)2, was synthesized. The synthesis of organic solvent soluble ThI4L2 (L = Et2O, OPCy3, and OPPh3) are the first examples of crystallographically characterized neutral thorium tetraiodide materials beyond binary ThI4. To show the viability of ThI4(Et2O)2 as a starting material for organothorium chemistry (C5Me4H)3ThI was synthesized and crystallographically characterized. ",

keywords = "Plutonium, Actinide, Tetravalent, Octahedral, Phosphine oxide",

author = "Windorff, \{Cory J.\} and Goodwin, \{Conrad A. P.\} and Sperling, \{Joseph M.\} and Albrecht-Sch{\"o}nzart, \{Thomas E.\} and Zhuanling Bai and Evans, \{William J.\} and Huffmann, \{Zachary K.\} and Renaud Jeannin and Long, \{Brian N.\} and Mills, \{David P.\} and Poe, \{Todd N.\} and Ziller, \{Joseph W.\}",

year = "2023",

month = oct,

day = "24",

doi = "10.1021/acs.inorgchem.3c02575",

language = "English",

journal = "Inorganic Chemistry ",

issn = "0020-1669",

publisher = "American Chemical Society",

}

TY - JOUR

T1 - Stabilization of Pu(IV) in PuBr4(OPCy3)2 and Comparisons with Structurally Similar ThX4(OPR3)2 (R = Cy, Ph) Molecules

AU - Windorff, Cory J.

AU - Goodwin, Conrad A. P.

AU - Sperling, Joseph M.

AU - Albrecht-Schönzart, Thomas E.

AU - Bai, Zhuanling

AU - Evans, William J.

AU - Huffmann, Zachary K.

AU - Jeannin, Renaud

AU - Long, Brian N.

AU - Mills, David P.

AU - Poe, Todd N.

AU - Ziller, Joseph W.

PY - 2023/10/24

Y1 - 2023/10/24

N2 - The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., "PuBr3(OPR)3," instead led to the isolation of the tetravalent trans PuIVBr4(OPCy3)2, PuBr/Cy, compound by spontaneous oxidation of PuIII. Generally, binary PuIV halides are unstable in both solution- and solid-state compounds. The donating nature of phosphine oxides has allowed the isolation and characterization of PuBr/Cy by crystallographic, multi-nuclear NMR, solid state and solution phase UV-vis-NIR spectroscopic techniques. The presence of a putative plutonyl(VI) complex formulated as "trans-PuVIO2Br2(OPCy3)2" was also observed spectroscopically and tentatively observed by single-crystal X-ray diffraction as a co-crystal of PuBr/Cy. A series of transThX4(OPCy3)2 (X = Cl, ThCl/Cy; Br, ThBr/Cy; I, ThI/Cy) complexes were synthesized for comparison to PuBr/Cy. The triphenylphosphine oxide, OPPh3, complexes trans-AnI4(OPPh3)2, (An = Th, ThI/Ph; U, UI/Ph) were also synthesized for comparison completing the series transUX4(OPPh3)2 (X = Cl, Br, I), UX/Ph. To enable the synthesis of ThI/Cy and ThI/Ph, a new nonaqueous thorium-iodide starting material, ThI4(Et2O)2, was synthesized. The synthesis of organic solvent soluble ThI4L2 (L = Et2O, OPCy3, and OPPh3) are the first examples of crystallographically characterized neutral thorium tetraiodide materials beyond binary ThI4. To show the viability of ThI4(Et2O)2 as a starting material for organothorium chemistry (C5Me4H)3ThI was synthesized and crystallographically characterized.

AB - The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., "PuBr3(OPR)3," instead led to the isolation of the tetravalent trans PuIVBr4(OPCy3)2, PuBr/Cy, compound by spontaneous oxidation of PuIII. Generally, binary PuIV halides are unstable in both solution- and solid-state compounds. The donating nature of phosphine oxides has allowed the isolation and characterization of PuBr/Cy by crystallographic, multi-nuclear NMR, solid state and solution phase UV-vis-NIR spectroscopic techniques. The presence of a putative plutonyl(VI) complex formulated as "trans-PuVIO2Br2(OPCy3)2" was also observed spectroscopically and tentatively observed by single-crystal X-ray diffraction as a co-crystal of PuBr/Cy. A series of transThX4(OPCy3)2 (X = Cl, ThCl/Cy; Br, ThBr/Cy; I, ThI/Cy) complexes were synthesized for comparison to PuBr/Cy. The triphenylphosphine oxide, OPPh3, complexes trans-AnI4(OPPh3)2, (An = Th, ThI/Ph; U, UI/Ph) were also synthesized for comparison completing the series transUX4(OPPh3)2 (X = Cl, Br, I), UX/Ph. To enable the synthesis of ThI/Cy and ThI/Ph, a new nonaqueous thorium-iodide starting material, ThI4(Et2O)2, was synthesized. The synthesis of organic solvent soluble ThI4L2 (L = Et2O, OPCy3, and OPPh3) are the first examples of crystallographically characterized neutral thorium tetraiodide materials beyond binary ThI4. To show the viability of ThI4(Et2O)2 as a starting material for organothorium chemistry (C5Me4H)3ThI was synthesized and crystallographically characterized.

KW - Plutonium

KW - Actinide

KW - Tetravalent

KW - Octahedral

KW - Phosphine oxide

U2 - 10.1021/acs.inorgchem.3c02575

DO - 10.1021/acs.inorgchem.3c02575

M3 - Article

SN - 0020-1669

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -