The synthesis and structural characterization of novel transition metal fluorides
High purity KMF[sub 6] and K[sub 2]MF[sub 6] salts (M = Mo,Re, Ru, Os, Ir, Pt) are obtained from reduction hexafluorides. A rhombohedral unit cell is observed for KReF[sub 6]. 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 RuF[sub 4] is determined from X-ray synchrotron and neutron powder data. Unit cells based on theorthorhombic PdF[sub 4] type cell are derived from X-ray powder data for ReF[sub 4] and OsF[sub 4]. Fluoride ion capture from KAgF[sub 4] provides the thermally unstable trifluoride as a bright, red, diamagnetic solid. The structure solution of AgF[sub 3] and redetermination of the AuF[sub 3] structure from X-ray synchrotron and neutron powder data demonstrate that the two are isostnictural. Thermal decomposition product of AgF[sub 3] is the mixed valence compound Ag[sup II]Ag[sub 2][sup III]F[sub 8]. Several new salts containing the (Ag - F)[sub n][sup n+] chain cation are prepared. The first linear (Ag - F)[sub n][sup n+] chain is observed in AgF[sup +]BF[sub 4 [sup [minus]]] which crystallizes in a tetragonal unit. AgFAuF[sub 4] has a triclinic unit cell and is isostructural with CuFAuF[sub 4]. AgFAuF[sub 6] has an orthorhombic unit cell and appears to be isostructural with AgFAsF[sub 6]. A second mixed valence silver fluoride, Ag[sup II]Ag[sup III]F[sub 5], is prepared, which magnetic measurements indicate is probably an AgF[sup +] salt. Magnetic data for all of the AgF[sup +] 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 O[sub 2] to O[sub 2][sup +]. Reactions with C[sub 6]F[sub 6] and C[sub 3]F[sub 6] suggest an electron capture mechanism for cationic AG(II) oxidations.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE; USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 7017272
- Report Number(s):
- LBL-32892; ON: DE93002551
- Resource Relation:
- Other Information: Thesis (Ph.D.)
- Country of Publication:
- United States
- Language:
- English
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The synthesis and structural characterization of novel transition metal fluorides
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
FLUORIDES
TRANSITION ELEMENT COMPOUNDS
BORON FLUORIDES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
GOLD FLUORIDES
IRIDIUM FLUORIDES
MAGNETIC PROPERTIES
MOLYBDENUM FLUORIDES
OSMIUM FLUORIDES
OXIDIZERS
PALLADIUM FLUORIDES
PLATINUM FLUORIDES
POTASSIUM FLUORIDES
RHENIUM FLUORIDES
RUTHENIUM FLUORIDES
SILVER FLUORIDES
TUNGSTEN FLUORIDES
ALKALI METAL COMPOUNDS
BORON COMPOUNDS
FLUORINE COMPOUNDS
GOLD COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
IRIDIUM COMPOUNDS
MOLYBDENUM COMPOUNDS
OSMIUM COMPOUNDS
PALLADIUM COMPOUNDS
PHYSICAL PROPERTIES
PLATINUM COMPOUNDS
POTASSIUM COMPOUNDS
REFRACTORY METAL COMPOUNDS
RHENIUM COMPOUNDS
RHENIUM HALIDES
RUTHENIUM COMPOUNDS
SILVER COMPOUNDS
SYNTHESIS
TUNGSTEN COMPOUNDS
400201* - Chemical & Physicochemical Properties