Hexafluorophosphate complexes

Vicentini and coworkers have reported the complexes of DPPA with lanthanide perchlorates 224), hexafluorophosphates 225), chlorides and nitrates 226). The anions in the perchlorate and hexafluorophosphate complexes are noncoordinated and hence the complexes are six coordinated. Conductance data for the nitrate complexes indicate that the coordination interaction between the lanthanide ion and the nitrate ion decreases along the lanthanide series 226). 

Rh(/ ,f )-1,2-bis /V-methyl(diphenylphosphino)amino cyclohexane-1,5-cyclohexadiene] hexafluorophosphate complex... 

Schubert, U., et al. (1999). Controlled polymerization of methyl methacrylate and ethyl acrylate using tris(4,4 -dimethyl-2,2 -bipyridine)copper(II) hexafluorophosphate complexes and aluminum isopropoxide. Polym. Bull., 43(4-5) 319-326. 

The crystal structure determination of sandwich 1 2 coronates with 15C5 has been attempted (Biinzli et al., 1985) but all the investigated complexes turned out to be completely disordered. The two coronates R(C104)3 (15C5)2, R= Nd, Eu, were found to be isomorphous. They crystallize in an I-centered lattice (Laue group 4/m for R = Eu). The luminescence spectrum of the Eu complex reveals the presence of three different metal sites, one of which having an inversion center. The hexafluorophosphate complex La(PFg)3 (15C5)2 crystallizes in an F-centered lattice. 

Pentamethylbenzene and anthracene react very rapidly with nitronium tetrafluoroborate in sulpholan to give cr-complexes, which decompose slowly (see below), and durene behaves similarly with nitronium hexafluorophosphate in acetonitrile. ... 

The hexafluorophosphates are among the most stable halogen complexes known. The highly symmetrical PF ion is stable to boiling aqueous alkaH and is decomposed only slowly in acidic solutions at ambient temperatures. It does hydrolyze rapidly at elevated temperatures in acid (85). The stabiHty of the PF 3 ion can be compared to the isoelectronic SF. The hexafluorophosphates can be decomposed yielding PF although in many cases only at temperatures where the PF reacts with the metal containers. Benzenediazonium hexafluorophosphate can be decomposed to PF, N2, and fluorobenzene at 120°C (86) and is a convenient source for laboratory amounts of PF as well as a frequently used catalyst. 

Anhydrous silver hexafluorophosphate [26042-63-7] AgPF, as well as other silver fluorosalts, is unusual in that it is soluble in ben2ene, toluene, and xylene and forms 1 2 molecular crystalline complexes with these solvents (91). Olefins form complexes with AgPF and this characteristic has been used in the separation of olefins from paraffins (92). AgPF also is used as a catalyst. Lithium hexafluorophosphate [21324-40-3] LiPF, as well as KPF and other PF g salts, is used as electrolytes in lithium anode batteries (qv). 

These compounds perform a dual function in synthesis procedures. The introduction of a complex anion assists in the stabilization of the desired product and the generation of unique intermediates by chloride displacement, eg, silver hexafluorophosphate, AgPF, forms adducts with neutral diamagnetic organometaHics which can act as controUed sources of highly reactive cations (29). Silver hexafluoroantimonate, AgSbF, is an electrophilic... 

Reaction of [Ir(rj -cod)(/x-pz)]2 with nitrosyl tetrafluoroborate yields 140 (L2 = cod), the cationic nitrosyl complex [85JCS(CC)908]. The 3-methylpyra-zolato complex reveals the same type of behavior, while 3,5-dimethylpyrazolato derivatives give a different kind of product Oxidation of [Ir( j -cod)(/i,-pz )]2 with nitrosyl tetrafluoroborate or hexafluorophosphate leads to 141 (X = BF4, PFg). 

Cyclization takes place when tert-butylisocyanide, benzaldehyde, anilinium chloride, and carbonyl(dicyano)cyclopentadienyl ferrate are reacted, the carbene complex 42 being the result (95JOM(491)135). /50-butyraldehyde, tert-butyl isocyanide, ammonium hexafluorophosphate, and [(T -Cp)Fe(CO)(CN)2] give the cationic bis-carbene 43. 

The N-coordinated compound [AuCljL] (L= l-ethyl-2-phenylimidazole) with silver tetrafluoroborate gives the cycloaurated species 102, which on further reaction with triphenylphosphine and sodium tetrafluoroborate or ammonium hexafluorophosphate forms the cationic complexes 103 (X = BF., PF,) (00JCS(D)271). 

The first diazonium-salt-crown-ether adduct was isolated and identified as a 1 1 complex by Haymore et al. (1975). Unfortunately Haymore never published the X-ray structural analysis of benzenediazonium hexafluorophosphate with 18-crown-6 which he performed in 1980. ORTEP drawings with measured bond angles and lengths from Haymore s investigation can be found in a review chapter by Bartsch (1983, p. 893). A few data from Haymore s work (e.g., R = 0.064) were also mentioned by Cram and Doxsee (1986, footnote 7). Groth (1981) published the results of his X-ray investigation of 4-methoxybenzenediazonium tetrafluoroborate and 21-crown-7 (R = 0.042) and Xu et al. (1986) those of 4-methoxybenzenediazonium tetrafluoroborate and dibenzo-24-crown-8 (R = 0.086). 

Fe(mtz)J(PF6)2. The solid iron(II) complex hexafluorophosphate of the ligand mtz = 1-methyltetrazole shows a gradual transition which is... 

A carbon-iron bond is also formed by the reaction of the cyclopropenium salt 185 with dicarbonyl(i/5-cyclopentadienyl)(trimethylsilyl)iron [92], (Scheme 69) In the reaction with benzocyclobutenylidene- 5-cyclopentadienyliron(II) hexafluorophosphate 186, CpFe(CO)2R (R=cyelo-C3H5, CH2-cyclo-C3H5) is converted to the allene and butadiene complexes, 187 and 188, respectively [93]. (Scheme 70)... 

In spite of the fact that silver(i) X-heterocyclic carbene complexes were widely employed as carbene-transfer reagents for the synthesis of other transition metal carbene complexes, their synthesis could also be achieved by the reaction of silver salts with relatively more labile carbene metal complexes, albeit rare. Complexes 71a-71c were reported to be synthesized from the reaction of the corresponding pentacarbonyl(carbene)chromium(i) complexes with silver(i) hexafluorophosphate in CDC13 under inert atmosphere (Scheme 17).117... 

Decomplexation of some metal complexes calls for drastic conditions. This is true for (/7-arene)(/7-cyclopentadienyl)iron(II) hexafluorophosphates, [FeAr(Cp)][PF6] [54, 55]. Although their chemical decomplexation is known [55 a], the most widely used method is pyrolytic sublimation at high temperatures (>200 °C) [55 b]. To evaluate MW irradiation as the method of decomplexation of such iron complexes, Roberts et al. performed the reaction in the presence of graphite [54]. They discovered that the yield of the free ligand from the [Fe( -N-phenylcarbazole)( -Cp)][PF6] complex (43) depended on the kind (flakes or powder) and amount of graphite, and on the irradia-... 

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