Nitrosyl, nitryl and dioxygenyl hexafluoroplatinate(IV) and (V) and related compounds: Synthesis, reactions and raman spectra
1975; Elsevier BV; Volume: 6; Issue: 6 Linguagem: Inglês
10.1016/s0022-1139(00)81692-9
ISSN1873-3328
AutoresJames E. Griffiths, W. A. Sunder,
Tópico(s)Inorganic Chemistry and Materials
ResumoAbstract The reactions of PtF 5 , O 2 PtF 6 , PtF 6 , IrF 6 , NOPtF 6 , NO 2 PtF 6 , NOIrF 6 and NO 2 IrF 6 with NOF and NO 2 F have been examined under a variety of conditions. The relative ease of synthesis of NOPtF 6 , (NO) 2 PtF 6 , NOIrF 6 and NO 2 IrF 6 and the conversion of NOIrF 6 to NOPtF 6 with PtF 6 confirms the order of strong oxidizing properties of Pt VI F 6 , Ir VI F 6 , Pt V F - 6 and Ir V F - 6 . The NO + 2 ion is intrinsically unstable with respect to the elimination of oxygen in Pt (IV) and Ir (IV) fluorometallate salts and accordingly there is serious doubt about earlier claims for the synthesis of the (NO + )(NO + 2 )PtF 6 salt. No evidence for the (NO 2 ) 2 PtF 6 could be found. Raman spectral data for NOBF 4 , NO 2 BF 4 , NO 2 AsF 6 , NOPtF 6 , NO 2 PtF 6 , (NO) 2 PtF 6 , NOIrF 6 , NO 2 IrF 6 and (NO) 2 IrF 6 are presented and analyzed. The NO + 2 ion appears to be linear in all of the compounds and the absence of the Raman forbidden ν 2 fundamental indicates little if any anion-cation interaction at least of the type that leads to a permanent distortion of the cation. In the spectra of all of the nitryl salts, including NO 2 BF 4 , a low frequency band at about 140 cm -1 is clearly observed, the intensity and shape of which is a function of the anion. The band probably reflects an unknown lattice dynamic process. No such bands are evident in the spectra of NO + and (NO + ) 2 salts.
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