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Title: Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

Abstract

A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} revealmore » small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.« less

Authors:
; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Chemical Sciences Division
OSTI Identifier:
982917
Report Number(s):
LBNL-3117E
Journal ID: ISSN 0020-1669; ISSN 1520-510X; TRN: US201014%%121
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 49; Journal Issue: 4; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37; ABSORPTION; ABSORPTION SPECTROSCOPY; ACTINIDES; BENCHMARKS; BONDING; ELECTRONIC STRUCTURE; RADICALS; SYNTHESIS; URANIUM; VALENCE

Citation Formats

Schelter, Eric J, Wu, Ruilian, Veauthier, Jacqueline M, Bauer, Eric D, Booth, Corwin H, Thomson, Robert K, Graves, Christopher R, John, Kevin D, Scott, Brian L, Thompson, Joe D, Morris, David E, and Kiplinger, Jaqueline L. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands. United States: N. p., 2010. Web. doi:10.1021/ic9024475.
Schelter, Eric J, Wu, Ruilian, Veauthier, Jacqueline M, Bauer, Eric D, Booth, Corwin H, Thomson, Robert K, Graves, Christopher R, John, Kevin D, Scott, Brian L, Thompson, Joe D, Morris, David E, & Kiplinger, Jaqueline L. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands. United States. doi:10.1021/ic9024475.
Schelter, Eric J, Wu, Ruilian, Veauthier, Jacqueline M, Bauer, Eric D, Booth, Corwin H, Thomson, Robert K, Graves, Christopher R, John, Kevin D, Scott, Brian L, Thompson, Joe D, Morris, David E, and Kiplinger, Jaqueline L. Wed . "Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands". United States. doi:10.1021/ic9024475. https://www.osti.gov/servlets/purl/982917.
@article{osti_982917,
title = {Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands},
author = {Schelter, Eric J and Wu, Ruilian and Veauthier, Jacqueline M and Bauer, Eric D and Booth, Corwin H and Thomson, Robert K and Graves, Christopher R and John, Kevin D and Scott, Brian L and Thompson, Joe D and Morris, David E and Kiplinger, Jaqueline L},
abstractNote = {A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.},
doi = {10.1021/ic9024475},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 4,
volume = 49,
place = {United States},
year = {2010},
month = {2}
}