V(SO3CF3)3, VO(SO3CF3)2 and VO(SO3CF3)3 have been prepared by reacting V(O2CCF3)3, VO(O2CCF3)2 and VOC13 with HSO3CF3. The i.r. data suggest a bridging bidentate nature for SO3CF3 groups. The diffuse reflectance spectrum of V(SO3CF3)3 suggests hexacoordination of vanadium, whilst that of VO(SO3CF3)2 is comparable to either five or six coordinated oxovanadium (IV) systems. The magnetic moments of V(SO3CF3)3 and VO(SO3CF3)2 are slightly lower than the spin-only values. Thermal decomposition of these triflates is simple. All the three triflates form coordination complexes with pyridine, 2, 2′-bipyridyl and triphenylphosphine oxide. 相似文献
Preparation and Spectroscopic Characterization of Perfluoro(isopropyl)-trifluoroacetylperoxide (CF3)2C(F)OOC(O)CF3 The reaction of perfluoroacetone (CF3)2CO with OF2 in a ratio 2 : 1 yields Perfluoro(isopropyl)-trifluoroacetylperoxide (CF3)2C(F)OOC(O)CF3. The reaction only occurs under CsF-catalysis. (CF3)2C(F)OOC(O)CF3 is characterized by vibrational, nmr and mass spectra. Using an excess of OF2 does not give any stable product. 相似文献
(CF3)2AsX (X = F, Cl) give at elevated temperatures substitution reactions with (CF3)2NO to afford (CF3)2NOAs(CF3)X and (CF3)2NOCF3. The formation of addition products at low temperatures to give [(CF3)2NO]2As(CF3)2X, followed by elimination reactions at elevated temperatures to give the final products provide for the first time direct evidence for the mechanisms of the substitution reactions. With (CF3)2AsBr, bromine was initially displaced to afford (CF3)2NOAs(CF3)2, followed by addition reactions to give [(CF3)2NO]3As(CF3)2. 相似文献
Perfluorosalkyl Tellurium Compounds: Oxidation of (CF3)2Te; Preparations and Properties of (CF3)2TeCl2, (CF3)2TeBr2, (CF3)2Te(ONO2)2, and (CF3)2TeO From the oxidation of (CF3)2Te with Cl2, Br2, O2, and ClONO2 the new trifluoromethyl tellurium compounds (CF3)2TeCl2, (CF3)2TeBr2, (CF3)2TeO, and (CF3)2Te(ONO2)2 are prepared. The 19F, 13C and 125Te n.m.r. spectra, the vibrational and mass spectra as well as the chemical properties of these compounds are described. By variation of the reaction conditions CF3TeCl3 and CF3TeBr3 are also formed. It has not been possible to isolate (CF3)2TeI2, but there is some evidence that it is formed as an intermediate. (CF3)2Te reacts with ozone to a very unstable compound, which decomposes at low temperature. 相似文献
Reactions of ClS[OCH(CF3)2]3 and S[OCH(CF3)2]2 with Phosphorus(III) Derivatives The sulfurane ClS[OCH(CF3)2]3 reacts with Me3P to give the phosphonium salt [Me3POCH(CF3)2]+Cl?, in the case of (MeO)3P products of an Arbuzov reaction are found: (MeO)2P-(:O)OCH(CF3)2 and MeCl; the sulfurane is reduced to the sulfoxylate S[OCH(CF3)2]2. The cyclic phosphite FP[OC(CF3)2C(CF3)2O] and P[OCH(CF3)2]3 furnish derivatives of pentacoordinated phosphorus upon reaction with ClS[OCH(CF3)2]3. The sulfoxylate S[OCH(CF3)2]2 oxidises Me3P, (MeO)3P and P[OCH(CF3)2]3 to form R3P? O and R3P? S (R = Me, OMe, OCH(CF3)2). The ether (CF3)2CHOCH(CF3)2 is isolated, too. 相似文献
O-Nitrosobis(trifluoromethyl)hydroxylamine gives novel reactions with tris(trifluoromethyl)-phosphine, -arsine and -stibine to affford mainly the corresponding bis(trifluoromethyl)nitroxol derivatives. Tris(trifluoromethyl) phosphine affords (CF3)2NOP(O)(CF3)2 and (CF3)2NNO. Tris(trifluoromethyl) arsine also gives (CF3)2NNO in high yield, together with smaller amounts of (CF3)2NOAs(CF3)2, CF3NCF2, COF2 and a polymeric white solid. With tris(trifluoromethyl)stibine, no oxidation nor addition reactions occurred. Instead, [(CF3)2NO]3Sb and [(CF3)NO]2SbCF3 were obtained in high yields. The stoichiometry of the reactions suggests that the additional amounts of bis(trifluoromethyl)nitroxyl groups bonded to antimony are derived from the trifluoromethyl groups bonded to antimony. Mechanisms to rationalise these reactions are proposed. 相似文献
Complexes of formula (η-C5H52Rh2{CF3C2CF3 · RNCO} have been prepared by three methods, from reactions between organic isocyanates and (η-C5H5)2Rh2(CO)(CF3C2CF3) or (η-C5H5)2Rh2(CO)2(CF3C2CF3); by treatment of (η-C5H5)2Rh2(CO)(CF3C2CF3) with organic azides; and by oxidation with Me3NO of the organic isocyanide in (η-C5H5)2Rh2(CO)(CNR)(CF3C2CF3). The crystal and molecular structure of the complex (η-C5H5)2Rh2{CF3C2CF3 · RNCO} with R = Ph has been determined from single crystal X-ray diffraction data. This reveals that the isocyanate has condensed with the hexafluorobut-2-yne to form an amide ligand of the form C(CF3)C(CF3)C(=O)N(R); this bridges the two rhodium atoms in a μ2η3-manner. 相似文献
Preparation and Properties of (CF3)2EMn(CO)5 (E ? P, As) The complexes (CF3)2EMn(CO)5 (E ? P, As) are formed by the reaction of E2(CF3)4 with HMn(CO)5. They can be converted quantitatively to the binuclear compounds [Mn(CO)4E(CF3)2]2 in a thermal (E ? P) or photochemical (E ? P, As) process. u. v. irradiation of a 1:1 mixture gives the mixed derivative Mn2(CO)8As(CF3)2P(CF3)2 together with the symmetrical systems. The Mn? E bond is less reactive with HBr and Me3SnBr than the M? E bond in derivatives of the type Me3ME(CF3)2 (M ? Si, Ge, Sn; Me ? CH3). The terminal (CF3)2E groups are found to be strong π-acceptor ligands. 相似文献
Trifluoronitrosomethane reacts with bis(trifluoromethyl)phosphine to give (CF3)2P(O)N(OH)CF3 and a small amount of (CF3)2NOH. On the other hand, the reactions with tris(trifluoromethyl)phosphine and bis(trifluoromethyl)chlorophosphine afford (CF3)2NOP(O)CF3N(CF3)2 and (CF3)2NP(O)(CF3)Cl respectively. Isomerisation of may be involved as found for the isomerisation of the phosphine, (CF3)2NOP(CF3)2, to the phosphoryl compound, (CF3)2NP(O)(CF3)2. Mechanisms for the above reactions are discussed. 相似文献
The reactions between bis(trifluoromethyl)nitroxyl and CF3PX2 (where X = F, Cl, Br and CN) in 2:1 molar ratio give addition products, [(CF3)2NO]2P(CF3)X2. The bromo and cyano products are unstable. The former decomposes at room temperature to give bromine and perfluoro-2-azapropene, and the latter yields predominantly (CF3)2NOCF3. With CF3PI2, iodine displacement occurs to afford [(CF3)2NO]2PCF3. On the other hand, P(CN)3 affords [(CF3)2NO]3PO, (CF3)2NON(CF3)2 and paracyanogen. Mechanisms for these reactions are proposed. 相似文献
N-(Trifluoromethylsulfonylimino)di-and-trifluoromethanesulfinimidoyl chlorides RS(=NSO2CF3)Cl (R = CF3, CHF2) react with potassium fluoride in 1,2-dimethoxyethane with formation of the corresponding N,N′-bis(trifluoromethylsulfonyl)fluoromethanesulfinimidamide potassium salts RS(=NSO2CF3)NSO2CF3?K. Analogous methanesulfinimidoyl and fluoromethanesulfinimidoyl chlorides (R = CH3, CH2F) fail to react with KF under similar conditions. Treatment of trifluoromethanesulfenamides CF3SNR2 with N,N-dichlorotrifluoromethanesulfonamide CF3SO2NCl2 leads to N,N-disubstituted N′-(trifluoromethylsulfonyl)trifluoromethanesul-finimidamides CF3S(=NSO2CF3)NR2. The reaction of N,N-dimethyl-N′-(trifluoromethylsulfonyl)trifluoromethanesulfinimidamide (R = CH3) with gaseous hydrogen chloride in diethyl ether gives sulfinimidoyl chloride CF3S(=NSO2CF3)Cl which could not be obtained by imination of CF3SCl. 相似文献
The insertion of (CF3)2CO into the PH bond of MenH3?nP yields MenH2?nPC(CF3)2OH and MenH1?nP[C(CF3)2OH]2 (n=O, 1), respectively [1]. MeP[C(CF3)2OH]2 rearranges giving the diphosphine [MePOCH(CF3)2]2 and the phosphorane MeP[OCH(CF3)2]4. Me2PH reacts with (CF3)2CO forming several products, e.g. MePF[OCH(CF3)2]2 and Me2PPMe2 [1]. The phosphines tBu(R)PH(R=Me, tBu), however, add (CF3)2CO giving rise to the phosphinites tBu(R)POCH(CF3)2, which furnish stable phosphonium salts upon treating with MeI. (CF3)2CO inserts into the SH bond of RSH to yield RSC(CF3)2OH (R=H,Me,Ph), which were reacted with MeI, too. Reacting SCl2 with LiOCH(CF3)2 gives S[OCH(CF3)2]2 which is oxidised by chlorine to the sulfurane ClS[OCH(CF3)2]3 [2]. The sulfurane is able to transfer (CF3)2CHO groups to phosphorus (III) compounds, e.g. P[OCH(CF3)2]3 and Me3P yielding P[OCH(CF3)2]5 and [Me3POCH(CF3)2]+Cl?. ClS[OCH(CF3)2]3 gives a stable salt upon reaction with SbCl5, like ClP[OCH(CF3)2]4. The mechanisms for these reactions are discussed. 相似文献
Bis(trifluoromethyl)nitroxyl gives oxidative addition products with (CF3)2PX (X = F, Cl, Br and CN). With (CF3(2PI, iodine is eliminated to afford (CF3)2NOP(CF3)2. Mechanisms for the reactions are proposed and discussed, and spectral data of new compounds presented. 相似文献
Syntheses and Characterizations of the First Tris and Tetrakis(trifluoromethyl) Palladates(II) and Platinates(II), [M(CF3)3(PPh3)]— and [M(CF3)4]2— (M = Pd, Pt) Tris(trifluoromethyl)(triphenylphosphino)palladate(II) and platinate(II), [M(CF3)3PPh3]—, and the tetrakis(trifluoromethyl)metallates, [M(CF3)4]2— (M = Pd, Pt), are prepared from the reactions of [MCl2(PPh3)2] and Me3SiCF3 / [Me4N]F or [I(CF3)2]— salts in good yields. [Me4N][M(CF3)3(PPh3)] crystallize isotypically in the orthorhombic space group Pnma (no. 62) with Z = 4. The NMR spectra of the new compounds are described. 相似文献
During the thermal decomposition of (CF3)2Cd and (CF3)2Zn complexes primarily difluorocarbene is eliminated. The formation of CF2 is unambiguously proved by matrix i.r. spectroscopy. Both (CF3)2Cd·D and (CF3)2Zn·D are excellent CF2 sources, which can easily be prepared and handled, and which undergo CF2 reactions even at low temperature. CF2 insertion was found during the reaction of (CF3)2Te with (CH3)2Cd via the intermediate formation of a CF3Cd compound to form CH3TeCF2CH3. (CF3)2Cd·glyme reacts with (CH3)3Si(OCOCF3) to CF3Cd(OCOCF3)·glyme; during this reaction CF2 is also eliminated. 相似文献
Bis(dimethylamino)trifluoro sulfonium Salts: [CF3S(NMe2)2]+[Me3SiF2]‐, [CF3S(NMe2)2]+ [HF2]‐ and [CF3S(NMe2)2]+[CF3S]‐ From the reaction of CF3SF3 with an excess of Me2NSiMe3 [CF3(NMe2)2]+[Me3SiF2]‐ (CF3‐BAS‐fluoride) ( 5 ), from CF3SF3/CF3SSCF3 and Me2NSiMe3 [CF3S(NMe2)2]+‐ [CF3S]‐ ( 7 ) are isolated. Thermal decomposition of 5 gives [CF3S(NMe2)2]+ [HF2]‐ ( 6 ). Reaction pathways are discussed, the structures of 5 ‐ 7 are reported. 相似文献
(CF3)2CN2 (1) and CF3CHN2 (4) react with (CF3)2CNSCl (2) to give (CF3)2CNSCCl(CF3)2 (3) and (CF3)2CNSCHClCF3 (5) respectively. From (4) and (NSCl)3 CF3CHNSCHClCF3 (6) and (8) are obtained. 相似文献
Reactions of Thiazyl Halides XSN (X = F, Cl) with Perfluorinated Imines Rf2 NH (Rf = F, CF3, CF3S, (CF3)2C?, (CF3)2S?): Attempted Preparations of Aminothiazyls (?N? S?N) Thiazyl halides or their precursors Cl3S3N3 and FC(O)N?SF2 react with perfluoro imines to provide the corresponding aminothiazyls as unstable and reactive intermediates. While with HNF2 or KF · HNF2 the final products N2F4 and S4N4 are formed, [(CF3)2N]2Hg reacts with Cl3S3N3 to give CF3N?CF2, FSN, and HgCl2. The expected product CF3SN?S?NSCF3 ( 4 ) is obtained from (CF3S)2NH or Hg[N(SCF3)2]2 and FSN probably via (CF3S)2 NSN. Surprisingly, (CF3)2C?NLi forms with ClSN, Cl3S3N3 or [S3N2Cl]Cl in the presence of NH4Cl 4,5-Dihydro-3,3,5,5-tetrakistrifluoromethyl-3H-1λ4,2,4,6-thiatriazine ( 6 ) and (CF3)2C?NSxN?C(CF3)2 (X = 1, 2) ( 7a, b ) as byproducts. A CsF catalyzed reaction at 70 to 80°C between (CF3)2C?NLi and FSN provides low yields of (CF3)2C?N? S? N?S?NCF(CF3)2 ( 8 ) together with 7a, b. The latter are the only products without CsF. When (CF3)2S?NH is treated with FSN, the compounds CF3SCF3, S4N4, and N2 are identified. It is shown by 19F and 14N-n.m.r. spectroscopy that (CF3)S?NSN is an unstable intermediate. 相似文献
The arsines and phosphines (CF3)2EN(CH3)2 (E= P or As) react with secondary amines with the formation of (CF3)2ENR2 and HN(CH3)2. Mechanistic and steric effects associated with these reactions are discussed. The influence of the groups (CF3)2E on the E-N-bonding and the reaction is examined. 相似文献
