Identifying Protonated Decavanadate Polyanions

Research Article| March 01, 2019 Identifying Protonated Decavanadate Polyanions Mark A. Cooper; Mark A. Cooper Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada Search for other works by this author on: GSW Google Scholar Frank C. Hawthorne; Frank C. Hawthorne § Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada §Corresponding author e-mail address: frank.hawthorne@umanitoba.ca Search for other works by this author on: GSW Google Scholar Anthony R. Kampf; Anthony R. Kampf Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA Search for other works by this author on: GSW Google Scholar John M. Hughes John M. Hughes Department of Geology, University of Vermont, Burlington, Vermont 05405, USA Search for other works by this author on: GSW Google Scholar The Canadian Mineralogist (2019) 57 (2): 245–253. https://doi.org/10.3749/canmin.1800069 Article history first online: 26 Mar 2019 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Mark A. Cooper, Frank C. Hawthorne, Anthony R. Kampf, John M. Hughes; Identifying Protonated Decavanadate Polyanions. The Canadian Mineralogist 2019;; 57 (2): 245–253. doi: https://doi.org/10.3749/canmin.1800069 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyThe Canadian Mineralogist Search Advanced Search Abstract The decavanadate anion, [V10O28]6−, is a common constituent in vanadate minerals and synthetic materials, and both protonated, [HxV10O28](6−x)−, and mixed-valent, [(V4+xV5+10−x)O28](6+x)−, varieties also occur. Here we examine recent structure refinements containing protonated decavanadates in order to develop simple criteria to help identify specific OD atom(s) belonging to (OH) groups of the decavanadate polyanion. Non-protonated O atoms on the surface of the decavanadate polyanion (i.e., [1]-, [2]-, and [3]-coordinated O atoms) have incident bond-valence sums from V atoms in the range ∼1.7–2.0 vu. Protonated O atoms on the exterior have incident bond-valence sums from V atoms in the range ∼1.2–1.5 vu and are either [3]-coordinated or [2]-coordinated by V atoms. All hydrogen bonds are directed toward a neighboring decavanadate polyanion in which the OA (acceptor) anions are 2.61–3.08 Å from their respective OD (donor) anions on the adjacent polyanion, and there is a linear relation between the OD…OA distance and the incident bond-valence received by OD from the bonded V atoms. For well-refined structures, the incident bond-valence sums from V atoms and the associated OD…OA distances suffice to identify protonation of the decavanadate polyanion and the specific anion(s) that is (are) protonated. These criteria show that one structure reported as protonated is not protonated, and one structure reported as containing a mixed V4+/5+ protonated decavanadate polyanion contains only V5+ and is not protonated, and another structure also reported as containing a mixed V4+/5+ protonated decavanadate polyanion contains both V4+ and V5+ but is not protonated. You do not have access to this content, please speak to your institutional administrator if you feel you should have access.