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Title: Strategic Capture of the {Nb7} Polyoxometalate

Abstract

Abstract Group V Nb‐polyoxometalate (Nb‐POM) chemistry generally lacks the elegant pH‐controlled speciation exhibited by group VI (Mo, W) POM chemistry. Here three Nb‐POM clusters were isolated and structurally characterized; [Nb 14 O 40 (O 2 ) 2 H 3 ] 14− , [((UO 2 )(H 2 O)) 3 Nb 46 (UO 2 ) 2 O 136 H 8 (H 2 O) 4 ] 24− , and [(Nb 7 O 22 H 2 ) 4 (UO 2 ) 7 (H 2 O) 6 ] 22− , that effectively capture the aqueous Nb‐POM species from pH 7 to pH 10. These Nb‐POMs illustrate a reaction pathway for control over speciation that is driven by counter‐cations (Li + ) rather than pH. The two reported heterometallic POMs (with UO 2 2+ moieties) are stabilized by replacing labile H 2 O/HO−Nb=O with very stable O=U=O. The third isolated Nb‐POM features cis ‐yl‐oxos, prior observed only in group VI POM chemistry. Moreover, with these actinide‐heterometal contributions to the burgeoning Nb‐POM family, it now transects all major metal groups of the periodic table.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Oregon State Univ., Corvallis, OR (United States)
  2. Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
  3. Universitat Rovira (Spain); Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
Publication Date:
Research Org.:
Oregon State Univ., Corvallis, OR (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1611515
Alternate Identifier(s):
OSTI ID: 1542479
Grant/Contract Number:  
SC0010802
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 45; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Martin, Nicolas P., Petrus, Enric, Segado, Mireia, Arteaga, Ana, Zakharov, Lev N., Bo, Carles, and Nyman, May. Strategic Capture of the {Nb7} Polyoxometalate. United States: N. p., 2019. Web. doi:10.1002/chem.201902770.
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Martin, Nicolas P., Petrus, Enric, Segado, Mireia, Arteaga, Ana, Zakharov, Lev N., Bo, Carles, & Nyman, May. Strategic Capture of the {Nb7} Polyoxometalate. United States. https://doi.org/10.1002/chem.201902770
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Martin, Nicolas P., Petrus, Enric, Segado, Mireia, Arteaga, Ana, Zakharov, Lev N., Bo, Carles, and Nyman, May. Tue . "Strategic Capture of the {Nb7} Polyoxometalate". United States. https://doi.org/10.1002/chem.201902770. https://www.osti.gov/servlets/purl/1611515.
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@article{osti_1611515,
title = {Strategic Capture of the {Nb7} Polyoxometalate},
author = {Martin, Nicolas P. and Petrus, Enric and Segado, Mireia and Arteaga, Ana and Zakharov, Lev N. and Bo, Carles and Nyman, May},
abstractNote = {Abstract Group V Nb‐polyoxometalate (Nb‐POM) chemistry generally lacks the elegant pH‐controlled speciation exhibited by group VI (Mo, W) POM chemistry. Here three Nb‐POM clusters were isolated and structurally characterized; [Nb 14 O 40 (O 2 ) 2 H 3 ] 14− , [((UO 2 )(H 2 O)) 3 Nb 46 (UO 2 ) 2 O 136 H 8 (H 2 O) 4 ] 24− , and [(Nb 7 O 22 H 2 ) 4 (UO 2 ) 7 (H 2 O) 6 ] 22− , that effectively capture the aqueous Nb‐POM species from pH 7 to pH 10. These Nb‐POMs illustrate a reaction pathway for control over speciation that is driven by counter‐cations (Li + ) rather than pH. The two reported heterometallic POMs (with UO 2 2+ moieties) are stabilized by replacing labile H 2 O/HO−Nb=O with very stable O=U=O. The third isolated Nb‐POM features cis ‐yl‐oxos, prior observed only in group VI POM chemistry. Moreover, with these actinide‐heterometal contributions to the burgeoning Nb‐POM family, it now transects all major metal groups of the periodic table.},
doi = {10.1002/chem.201902770},
journal = {Chemistry - A European Journal},
number = 45,
volume = 25,
place = {United States},
year = {Tue Jun 18 00:00:00 EDT 2019},
month = {Tue Jun 18 00:00:00 EDT 2019}
}
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https://doi.org/10.1002/chem.201902770
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    Two synthetic routes generate two isopolyoxoniobates based on {Nb 16 } and {Nb 20 }
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