The peroxy radicals CF3OO and FC(O)OO are prepared in high yields by vacuum flash pyrolysis of ROONO2 or ROOOR (R=CF3, FC(O)), highly diluted in inert gases, and subsequent isolation in inert-gas matrices by quenching the product mixtures at low temperatures. The IR spectrum of FC(O)OO was observed for the first time and eight fundamentals as well as several combinations were measured and assigned for both cis and trans rotamers of FC(O)OO. Discrepancies in an earlier assignment of the fundamentals of CF3OO have been eliminated and its IR spectrum is reported fully. The matrix UV spectra of both peroxy radicals (X2A"--> 2(2)A" transition) are in agreement with the gas-phase spectra; however, there are differences in the absorption cross-sections, for which possible reasons are discussed. The X2A"--> 1(2)A' transitions in the near IR region are too weak to be detected with our instrumentation.

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The reaction of the Pt complexes cis-[Pt-(CH 3 ) 2 {R 2 P(Ind)} 2 ] (Ind = 2-(3-methyl)indolyl, R = Ph (1 a), 4-FC 6 H 4 (1 b), 4-CF 3 C 6 H 4 (1 c)) with HF afforded the fluorido complexes trans-[Pt(F(HF) 2 )(CH 3 ){R 2 P-(Ind)} 2 ] 2 a-c, which can be converted into trans-[Pt(F)-(CH 3 ){R 2 P(Ind)} 2 ] (3 a-c) by treatment with CsF. Addition of 3-hexyne to 2 a-c gave alkyne complexes trans-[Pt(C,C-η 2 -C 2 H 5 C�CC 2 H 5 )(CH 3 ){R 2 P(Ind)} 2 {F(HF) 2 }] (4 a-c) at which a fluoride is stabilised as polyfluoride in the coordination sphere by hydrogen bonding to the indolyl-substituted phosphine ligands. Subsequent heating of a solution of 4 a in the presence of PVPHF led to fluoroalkene formation. Selective catalytic hydrofluorination of alkynes to yield (Z)-fluoroalkenes were developed. The ability of hydrogen bonding to polyfluoride favours the fluorination step as demonstrated by studies with complexes bearing no indolyl groups at the phosphine ligands.

The reaction of [PtCl 2 (COD)] (COD = 1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr 2 P-(C 9 H 8 N)) led to the formation of the platinum(ii) chlorido complexes, cis-[PtCl 2 {iPr 2 P(C 9 H 8 N)} 2 ] (1) and trans-[PtCl 2 {iPr 2 P-(C 9 H 8 N)} 2 ] (2). The cis-complex 1 reacted with NEt 3 yielding the complex cis-[PtCl{k 2 -(P,N)-iPr 2 P(C 9 H 7 N)}{iPr 2 P(C 9 H 8 N)}] (3) bearing a cyclometalated k 2 -(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt 3 . Treatment of 1 or 3 with (CH 3 ) 4 NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{k 2 -(P,N)-iPr 2 P(C 9 H 7 N)} 2 ] (4). The molecular structures of the complexes 1-4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF {k 2 -(P,N)-iPr 2 P(C 9 H 7 N)}{iPr 2 P(C 9 H 8 N)}] • (HF) 4(5 • (HF) 4 ) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii) fluorido complex 5 • (HF) 4 exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3, complex 5 • (HF) 4 reacted with CO or the ynamide 1-(2phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){k 2 -(P,C)-iPr 2 P(C 9 H 7 NCO)}{iPr 2 P(C 9 H 8 N)}][F(HF) 4 ] (7) and a complex, which we suggest to be cis-[Pt{C = C(Ph)OCN(C 3 H 6 )} {k 2 -(P,N)-iPr 2 P(C 9 H 7 N)}{iPr 2 P(C 9 H 8 N)}][F(HF) 4 ] ( 9), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9.

Professor Josef Goubeau in memoriamInhaltsu È bersicht. Von verschiedenen Bildungsreaktionen fu È r CF 3 ONO 2 ist die Umsetzung von CF 3 OF mit NO 2 bei Raumtemperatur unter hohen Dru È cken zur pra È parativen Synthese geeignet. Das Produkt wird durch wiederholte fraktionierte Kondensation im Vakuum erstmals in reiner Form erhalten. CF 3 ONO 2 ist ein farbloses Gas mit einem Siedepunkt von ±18 ± 3°C (extrapol.) und einem Schmelzpunkt von ±163°C. Die Verbindung zerfa È llt in der Gasphase bei Raumtemperatur und auch bei tiefen Temperaturen in der flu È ssigen Phase langsam in CF 2 O und FNO 2 . Weiterhin ist CF 3 ONO 2 sowohl spektroskopisch durch NMR-, IR-, Raman-und UV-Spektroskopie, als auch strukturell durch Elektronenbeugung an der Gasphase und quantenchemische Rechnungen (B3LYP, MP2) charakterisiert. Die CF 3 ±O-Bindung liegt in der Ebene der NO 3 -Gruppe, die zentrale CF 3 O±NO 2 -Bindung ist mit 1.493(6) A Ê sehr lang. Die B3LYP/6-31G*-Rechnung reproduziert die experimentellen Struktur-und Schwingungsdaten gut. Trifluoromethyl Nitrate, CF 3 ONO 2Abstract. From different routes to CF 3 ONO 2 , the reaction of CF 3 OF with NO 2 at room temperature under high pressure is the most favorable to synthesize CF 3 ONO 2 in preparative scale. The pure product is isolated for the first time after repeated trap-to-trap condensation in vacuo. CF 3 ONO 2 is a colourless gas with a boiling point of ±18 ± 3°C (extrapol.) and a melting point of ±163°C. Trifluoromethyl nitrate decays slowly into CF 2 O and FNO 2 at room temperature in the gas phase as well as in the liquid state at lower temperatures. Furthermore, CF 3 ONO 2 is characterized spectroscopically by NMR, IR, Raman, and UV, and structurally by gas electron diffraction and quantum chemical calculations (B3LYP, MP2). The CF 3 ±O bond is in the plane of the NO 3 moiety, the central CF 3 O±NO 2 bond of 1.493(6) A Ê is very long. The B3LYP/6-31G* calculation reproduces best the experimental data.