The synthesis and structural characterization of novel transition metal fluorides

Thesis/Dissertation · Tue Sep 01 00:00:00 EDT 1992

DOI:https://doi.org/10.2172/10190395· OSTI ID:10190395

Casteel, Jr., William Jack ^[1]

---

1. Univ. of California, Berkeley, CA (United States)

High purity KMF₆ and K₂MF₆ salts (M = Mo,Re, Ru, Os, Ir, Pt) are obtained from reduction hexafluorides. A rhombohedral unit cell is observed for KReF₆. Fluoride ion capture by Lewis acids from the hexafluorometallate (IV) salts affords high purity tetrafluorides for M = Mo, Re, Ru, Os, and Pd. The structure of RuF₄ is determined from X-ray synchrotron and neutron powder data. Unit cells based on theorthorhombic PdF₄ type cell are derived from X-ray powder data for ReF₄ and OsF₄. Fluoride ion capture from KAgF₄ provides the thermally unstable trifluoride as a bright, red, diamagnetic solid. The structure solution of AgF₃ and redetermination of the AuF₃ structure from X-ray synchrotron and neutron powder data demonstrate that the two are isostnictural. Thermal decomposition product of AgF₃ is the mixed valence compound Ag^IIAg₂^IIIF₈. Several new salts containing the (Ag - F)$$n+\atop{n}$$ chain cation are prepared. The first linear (Ag - F)$$n+\atop{n}$$ chain is observed in AgF⁺BF_4- which crystallizes in a tetragonal unit. AgFAuF₄ has a triclinic unit cell and is isostructural with CuFAuF₄. AgFAuF₆ has an orthorhombic unit cell and appears to be isostructural with AgFAsF₆. A second mixed valence silver fluoride, Ag^IIAg^IIIF₅, is prepared, which magnetic measurements indicate is probably an AgF⁺ salt. Magnetic data for all of the AgF⁺ salts exhibit low magnitude, temperature independent paramagnetism characteristic of metallic systems. Cationic AG(II) in acidic AHF solutions is a powerful oxidizer, capable of oxidizing Xe to Xe(II) and O₂ to O₂⁺. Reactions with C₆F₆ and C₃F₆ suggest an electron capture mechanism for cationic AG(II) oxidations.

• Research Organization: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 10190395
• Report Number(s): LBL-32892; ON: DE93002551
• Resource Relation: Other Information: TH: Thesis (Ph.D.); PBD: Sep 1992
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
TRANSITION ELEMENT COMPOUNDS
FLUORIDES
POTASSIUM FLUORIDES
MOLYBDENUM FLUORIDES
RHENIUM FLUORIDES
OSMIUM FLUORIDES
IRIDIUM FLUORIDES
RUTHENIUM FLUORIDES
PLATINUM FLUORIDES
TUNGSTEN FLUORIDES
SILVER FLUORIDES
PALLADIUM FLUORIDES
BORON FLUORIDES
CRYSTAL STRUCTURE
MAGNETIC PROPERTIES
OXIDIZERS
CHEMICAL PREPARATION
GOLD FLUORIDES
400201
CHEMICAL AND PHYSICOCHEMICAL PROPERTIES