Chemical transformation of bis((perfluoroalkyl)sulfonyl)methanes and 1,1,3,3‐tetraoxopolyfluoro‐1,3‐dithiaycloalkanes

Halogenation of the potassium or silver salts of bis((trifluoromethyl)sulfonyl)methane(CF₃SO₂)₂CH₂ and its cyclo analogues (CF₂)_nSO₂‐CH₂SO₂CF₂ with N‐fluoro‐bis((trifluoromethyl)sul‐fonyl)imine (CF₃SO₂)₂NF, chlorine or bromine gave good yields of the corresponding α‐halo disulfones (CF₃SO₂)₂CHX and (CF₂)_nSO₂CHXSO₂CF₂ (X: F, Cl, Br; n = 1,2). Some chemical transformations of these fluorinated α‐halo‐disulfones are described. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 147–151, 1999     

Studies on sulfinatodehalogenation: XVII. The sulfinatodehalogenation of primary perfluoroalkyl iodides and bromides by Rongalite

Using acetonitrile or DMF as cosolvent, both perfluoroalkyl iodides such as Cl(CF₂)_nI (n = 4,6,8, la—lc ), CF₃ (CF₂)_n I (n = 5,6,7, ld—lf ), I (CF₂)_n O (CF₂) SO₃ Na(n = 2,4,6, lg—li ) and perfluoroalkyl bromides such as Cl (CF₂)_n Br (n = 4,6, 3a—3b ) and C₇F₁₅ Br (3e) reacted with Rongalite in aqueous solution to give the corresponding sulfinates Cl (CF₂)_n SO₂ Na (n = 4,6,8, 2a—2c ), CF₃-(CF₂)_nSO₂Na (n = 5,6,7, 2d—2f ) and NaO₂S(CF₂)_nO(CF₂)₂SO₃Na (n = 2,4,6, 2g—2i ) in moderate yields. 1 H-perfluoroalkanes were formed as the main products when other solvents such as ethanol. iso-propanol, 1,4-dioxane and morpholine were used.     

Preparation and properties of perfluorochloromethyl-mercaptophosphoryldichlorides and -chlorophosphanes

In Arbuzov-type reactions CF_nCl_3?nSCl reacts with ROPCl₂ (R = CH₃, C₂H₅) to give CF_nCl_3?nSP(O)Cl₂ (n = 3,2,1,0). The corresponding reaction with CF₃SeX (X = Cl, Br) produces CF₃SeP(O)Cl₂ in good yields only in the presence of catalysts such as SbCl₅ or BCl₃. Reactions between P₄ and the sulfenylchlorides produce (CF_nCl_3?nS)_xPCl_3?n (n = 3,2,1 and x = 1,2). On heating CF_n′ Cl_3?n′ SP(O)Cl₂ (n′ = 2,1,0) decompose to P(O)Cl₃ and SCF_n′ Cl_2?n′. During this process fluorination of P(O)Cl₃ to P(O)F₃ by SCF₂ is observed. A Cl/Br exchange between CF_nCl_3?nSP(O)Cl₂ (n = 3,2) and PBr₃ was proved ¹⁹F? and ³¹P-NMR-spectroscopically.Chemical and physical properties of the newly synthesized compounds will be discussed.     

Acetalization and Transacetalization Reactions Catalyzed by Ruthenium,Rhodium, and Iridium Complexes with {2‐{{Bis[3‐(trifluoromethyl)phenyl]phosphino}methyl}‐2‐methylpropane‐ 1,3‐diyl}bis[bis[3‐(trifluoromethyl)phenyl]phosphine] (MeC[CH2P(m‐CF3C6H4)2]3)

The complexes [RhCl_(3−n)(MeCN)_n(CF₃triphos)](CF₃SO₃)_n (n=1, 2; CF₃triphos=MeC[CH₂P(m‐CF₃C₆H₄)₂]₃) and [M(MeCN)₃ (CF₃triphos)](CF₃SO₃)_n (M=Ru, n=2; M=Ir, n=3) are catalyst precursors for some typical acetalization and transacetalization reactions. The activity of these complexes is higher than those of the corresponding species containing the parent ligand MeC[CH₂P(C₆H₅)₂]₃(Htriphos). Also the complexes [MCl₃(tripod)] (tripod=Htriphos and CF₃triphos) are active catalysts for the above reactions. The complex [RhCl₂(MeCN)(CF₃triphos)](CF₃SO₃) catalyzes the acetalization of benzophenone.     

Darstellung und Eigenschaften von Trifluormethylmercaptothiophosphoryldichlorid

Preparation and Properties of Trifluoromethylmercaptothiophosphoryldichloride The reaction of CF₃SP(O)Cl₂ with SPCl₃ leads to a CF₃S-chlorine exchange and gives CF₃SP(S)Cl₂ in 50% yield. A controlled hydrolysis of CF₃SP(O)Cl₂ affords CF₃SP(O)(OH)₂, that cannot be isolated as such, but it condenses to CF₃SP(O)(OH)O? [P(SCF₃)(O)? O]_nP(O)(OH)SCF₃. On the other hand, CF₃SP(S)Cl₂ reacts with water to yield H₃PO₄, CF₃SH, S₈, and HCl. CF₃SP(X)Cl₂ reacts with alcohols to give CF₃SP(X)(OR)₂ [R = CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₄H₉ and for X = O, R = C₆H₅, too]. The formation of semi-esters CF₃SP(X)Cl(OR′) could be proven for X = O, R′ = CH₃, C₆H₅ and for X = S, R′ = R. While CF₃SP(O)(OC₂H₅)₂ rapidly decomposes into SCF₂ and FP(O)(OC₂H₅)₂, the other compounds and primarily CF₃SP(O)(OCH₃)₂ and CF₃SP(S)(OR)₂ ar stable. The reaction between CF₃SCl and CH₃SPCl₂ results in CF₃SCH₂SPCl₂ and that between CF₃SP(O)Cl₂ and AlCl₃ gives [CF₃SP(O)Cl]⁺[AlCl₄]^?. Physical and spectroscopical data are given for the newly formed compounds.     

Studies on sulfinatodehalogenation: III. The sulfinatodeiodination of primary perfluoroalkyl iodides and α,ω-perfluoroalkylene diiodides by sodium dithionite

Using P. T. C. or cosolvents, both perfluoroalkyl iodides such as Cl(CF₂),_nI (n=2, 4, 6, 1a-1c), H(CF₂)₈I (1d), CF₃(CF₂)_nI (n=3, 5, 7, 1e-1g), and α. ω-perfluoroalkylene diiodides such as (ICF₂CF₂)₂O (4a), I (CF₂)_nI (n=6, 8, 10, 4b-4d) reacted smoothly with sodium dithionite in aqueous solution under mild conditions to give the corresponding perfluoroalkanesulfinates Cl(CF₂)_nSO₂Na (n=2, 4, 6, 2a-2c), H(CF₂)₈SO₂Na (2d), CF₃(CF₂)nSO₂Na (n=3, 5, 7, 2e-2g), α, ω-perfluoroalky-lenedisulfinates O (CF₂CF₂SO₂K)₂ (5a), and KO₂S(CF₂)_nSO₃K (n=6, 8, 10, 6b-6d) in moderate to high yields. These sulfinates were converted to the corresponding sulfonyl chlorides by reacting with chlorine in the usual way. Thus the discovery of the new reagent renders sulfinatodeiodination a practical method for the synthesis of perfluorosulfinic and perfluorosulfonic acids and their derivatives from the corresponding perfluoroalkyl iodides.     

Mono- and bis-alkoxides of tris(3,5-dimethylpyrazolyl)borato molybdenum and tungsten nitrosyls

The complexes [ML^*(NO)Cl(OR)] {L^* = HB(3,5-Me₂C₃HN₂)₃; M= Mo, R = CH₂CH₂X, X = Cl, OMe or OEt; (CH₂)_nOH, n = 2, 5, 6; M = W, R = CH₂CH₂X, X = Cl, OMe or OEt; (CH₂)_nOH, n = 2–6; CH₂(CF₂)₃CH₂OH; CHMeCH₂CMe₂OH} and [ML^*(NO)(OR)₂] {M = Mo, R = CH₂CH₂X, X = Cl, OMe or OEt; (CH₂)_nOH, n = 2–6; M = W,R = CH₂CH₂X, X= Cl, OMe or OEt; (CH₂)_nOH, n = 2,4–6; CH₂(CF₂)₃CH₂OH} have been prepared from [ML^*(NO)Cl₂] and the appropriate alcohol in the presence of NEt₃ or NaCO₃, and have been characterized by IR, ¹H NMR and mass spectroscopy.     

Dimethyl-N-Halogenamine,ihre Ammoniumsalze und Bortrihalogenid-Addukte

Dimethyl-N-Halogenoamine, their Ammonium Salts and Borontrihalide Adducts The preparation and vibrational spectra of (CH₃)₂NHCl⁺X^? (X^? = CF₃SO₃^? I , SO₃F^? II , SO₃Cl^? III , BCl₄^? IV ), and (CH₃)₂NHBr⁺CF₃SO₃^? V as well as the adducts (CH₃)₂NCl · S (S = BF₃ VI , BCl₃ VII , BBr₃ VIII ) and (CH₃)₂NBr · BF₃ IX are reported. The crystal structure of VII has been determined from three-dimensional diffractometer data at ?100°C. The Cl atom and one methyl group in the dimethyl-N-chloroamino group show disorder. The structural data are: B? Cl 183(2) pm, B? N 167(3) pm, N? C 152(3) pm (distances to disordered positions are not included).     

14/15N-NMR und 11B-NMR-Daten von Trifluormethylthioaminoboranen mit natürlicher Isotopenhäufigkeit

^14/15N N.M.R. and ¹¹B N.M.R. Data of Trifluoromethylthioamino-boranes with Natural Isotope Abundance (Part 2) ^14/15N as well as ¹¹B-NMR data for trifluoromethylthioabminoboranes of the types XnB[N(SCF₃)₂], with X = F, Cl, Br, N₃, or NHSCF₃, n = 0, 1 or 2, and Cl_3?nB(NHSCF₃)n with n = 1, 2 or 3, as well as for the amine-borne Me₃NBCl₂N(SCF₃)₂ and the cyclic borazene (CF₃SNHBNH)₃ are reported. These data are used, together with a qualitative analysis of the bonding situation based on observed rotational barriers and known structures, to analyse for B ← N back donation in these compounds. Relatively small variations in δ^14/15N compared to those observed for alkylaminoboranes as well as large variations in δ¹¹B are suggestive of small contributions only from back bonding. In addition the ?halogene like”? nature of the (CF₃S)₂N group is confirmed. For the series X₂BN(SCF₃)₂ (X = F, Cl, Br on N₃), XB[N(SCF₃)₂]₂ (X = Cl, Br, N₃ or N(SCF₃)₂) and Cl_n?3B(NHSCF₃)_n (n = 1, 2 or 3) a linear relationship for δ¹¹B and δ^14/15N is observed. It is furtheron demonstrated that hitherto known δ^14/15N/¹¹B correlations are valid only in case of strong B ← N back donation.     

Nitroxide chemistry. Part XVII [1]. Reaction of bistrifluoromethyl nitroxide with some halogenoalkanes and related alkenes

The mono (bistrifluoromethylamino-oxy)alkanes (CF₃)₂NOCXYZ (X = Y = F, Z = Cl; X = H, Y = F or Cl, Z = CH₃; X = Y = F, Z = CH₃; X = H, Y = Cl or Br, Z = CF₃; X = Cl, Y = Br, Z = CF₃) have been synthesised by treatment of appropriate halogenoalkanes, CHXYZ, with bistrifluoromethyl nitroxide. The 1,2-bis(bistrifluoromethylamino-oxy)alkanes (CF₃)₂NOCH₂CXYON(CF₃)₂ were obtained as by-products in the reactions involving the ethanes CH₃CHXY (X = H, Y = F or Cl; X = Y = F); these products, like their analogues (CF₃)₂NOCHFCF₂ON(CF₃)₂ and (CF₃)₂NOCH₂CCl₂ON(CF₃)₂, were also prepared $\text{via}$ attack of bistrifluoromethyl nitroxide on the corresponding ethenes.     

Unusual reactions of N-(trifluoromethylsulfonylimino)di-and-trifluoromethanesulfinimidoyl chlorides

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.     

Studies on sulfinatodehalogenation: IV. The sulfinatodebromination of primary perfluoroalkyl bromides and perfluoroalkylene α, ω-dibromides

Using PTC or cosolvent, both perfluoroalkyl bromides such as Br (CF₂)₂O(CF₂)₂SO₂Na ( 1 ), Br(CF₂)₂OCF₂CO₂H ( 2 ), Cl(CF₂)₄Br ( 3 ), Cl(CF₂Br ( 4 ), n-C₆F₁₃Br ( 5 ), n-C₈F₁₇Br ( 6 ), H(CF₂)₈Br ( 7 ), α, ω-dibromides O(CF₂CF₂Br)₂ ( 8 ), Br(CF₂)₆Br ( 9 ) and Br(CF₂)₈Br ( 10 ) reacted readily with Na₂S₂O₄ in the presence of NaHCO₃ in aqueous solution to form the corresponding perfluoroalkane sulfinates NaO₂S(CF₂)₂O(CF₂)₂SO₂Na ( 11 ), NaO₂S(CF₂)₂OCF₂CO₂Na ( 12 ), Cl(CF₂)₄SO₂Na ( 13 ), Cl(CF₂)₂SO₂Na ( 14 ), n-C₃F₁₃SO₂Na ( 15 ), n-C₈F₁₇SO₂Na ( 16 ), H(CF₂)₈SO₂Na ( 17 ), α, ω-disulfinates O(CF₂CF₂SO₂Na)₂ ( 18 ), NaO₂S(CF₂)₄SO₂Na ( 19 ) and NaO₂S(CF₂)₈SO₂Na ( 20 ) in 66—97% yields. To this new and general reaction of perfluoroalkyl bromides, the name sulfinatodebromination is proposed.     

Studies on sulfinatodehalogenation: IX. Synthesis and reaction of secondary perfluoroalkyl iodides

Several derivatives of secondary perfluoroalkyl iodides such as CF₃CFI(CF₂)₂O(CF₂)₃SO₂F (3), CF₃CFI(CF₂),O(CF₂)₂SO₃Na (4), CF₃CFI(CF₃)_n Cl (n=2, 7a; n=4, 7b) and CF₃(CF2)₂-OCFICF₃ (8) were synthesized using known methods, their reaction with sodium dithionite was studied and various olefins were added into the reaction system as radical traps to yield the 1:1 radical adducts.     

Bi-functional fluoroalkylation reagents: an introduction to halo-substituted 3-oxa-perfluoroalkanesulfonyl fluorides

X(CF₂CF₂)_nOCF₂CF₂SO₂F (X=I, Br, Cl; n=1, 2, 3, 4) are widely used fluoroalkylation reagents, which can incorporate ‘heavy’ fluorous tags into organic compounds. X(CF₂CF₂)_nOCF₂CF₂SO₂F have both sulfonyl and halo groups. They behave as bi-functional fluoroalkylation reagents. The cleavage of the C–I bonds of I(CF₂CF₂)_nOCF₂CF₂SO₂F by reductants (such as Na₂S₂O₄, Zn), single electron transfer reagents and radical initiator systems (like Bz₂O₂, AIBN, and (t-BuO)₂, or under UV and heat) gives, respectively, the sulfinatodehalogenated products, the hydrodehalogenated products, the homo-coupling products and the perfluoroalkylated products (if alkenes, alkynes or arenes were added). The functionalization of the sulfonyl groups (SO₂F) of X(CF₂CF₂)_nOCF₂CF₂SO₂F by esterification, amidation, and fluorination affords the corresponding perfluoroalkanesulfonates, fluoroalkanesulfonamide, and perfluoroalkanes. In many cases, both the halo and sulfonyl groups of X(CF₂CF₂)_nOCF₂CF₂SO₂F are transformed. These transformations finally lead to hundreds of useful highly fluorinated materials, such as supper acids, catalysts, surfactants, ion-exchange resins, electrolytes, polymers, and dense ionic liquids. Furthermore, X(CF₂CF₂)_nOCF₂CF₂SO₂F have commendable advantages, such as the easy preparation, the wide range of substrate tolerance, the mild reaction condition, and the high yields of desired products, which make them very promising. This review briefly summarizes the synthesis, reactivity, and applications of these intriguing reagents.     

(Trifluoromethyl)germanes. Preparation and properties of (CF3)2GeHX (X = H,D, F,Cl, Br,I, CH3) and CF3GeHnX3-n (X = H,D, CF2H,CH3)

The hydrogenation of (CF₃)_nGeX_4-n (X = halogen, n = 1–3) with NaBH₄ in an acidic medium has been investigated. Deuteration with NaBD₄ and D₃PO₄ gave the partially deuterated species CF₃GeH_nD_3-n and (CF₃)₂GeH_nD_2-n in reasonable isotopic purity. The (CF₃)₂GeHBr was isolated and converted into the halides (CF₃)₂GeHX (X = F, Cl, I) by treatment with AgX or HX. Insertion of CF₂ into a GeH bond has been observed, and (CF₃)(CF₂H)GeH₂ has been characterized. Direct alkylation of GeH bonds was brought about by reaction with a mixture of RI and R′₂Zn (R, R′= CH₃, C₂H₅), and the methyl(trif]uoromethyl)germanes CF₃GeH₂(CH₃), CF₃GeH(CH₃)₂ and (CF₃)₂GeH(CH₃) were isolated. For R = CD₃, R′ = CH₃ the product distribution can be accounted in terms of two competing mechanisms.     

A mass spectral study of some symmetric and unsymmetric sulfides,disulfanes, and trisulfanes

The low-resolution mass spectra of 13 trifluoromethyl and/or methyl sulfur-containing compounds (CF₃S_nCF₃, CF₃S_nCH₃, CH₃S_nCH₃, CF₃S_mCl, and CH₃S_mCl; n = 1, 2, 3; m = 1, 2) are reported and discussed. There is a considerable similarity between the fragmentation pattern of compounds with the same terminal groups. However, with a fluorinated and a non-fluorinated methyl group, the major fragmentation products produced are similar to those for the dimethyl compounds.     

Perfluormethyl-element-liganden XII. Zweikernkomplexe des rheniums: Re2(CO)8XY [1]

The reaction of Re₂(CO)₁₀ with E₂(CF₃)₄ (E = P, As) yields the binuclear complexes Re₂(CO)₈[E(CF₃)₂]₂ with two E(CF₃)₂ bridges. The complexes Re₂(CO)₈E(CF₃)₂I (E = P, As) and Re₂(CO)₈As(CF₃)₂Cl, containing two different bridges, are formed in the reactions of Re₂(CO)₁₀ with (CF₃)₂EI (E = P, As) and (CF₃)₂AsCl, respectively. A series of new binuclear complexes is obtained on substitution of iodine in the compounds Re₂(CO)₈E(CF₃)₂I (E = P, As) by SCH₃, SCF₃, SeCF₃, P(CH₃)₂ and H. The binuclear complexes Re₂(CO)₈(E′CF₃)₂ having two E′CF₃ bridges (E′ = S, Se) are obtained reacting Re(CO)₅I With Hg(E′CF₃)₂. At room temperature the mononuclear complex Re(CO)₅SeCF₃ is obtained. Substitution of iodine in Re₂(CO)₈I₂ by SCF₃ also yields the symmetrical compound Re₂(CO)₈(SCF₃)₂; reduction with NaBH₄ gives the binuclear hydride Re₂(CO)₈HJ. - IR and NMR spectra (¹H, ¹⁹F) of the new complexes are reported and discussed.     

The reactions of perfluoro- and α,α-dichloropolyfluoroalkanesulfinates

Sodium perfluoroalkanesulfinate, R_FSO₂Na [R_F?Cl(CF₂)₄, 1a; CF₃(CF₂)₅, 1b; Cl(CF₃)₆, 1c] reacted with bromine in aqueous solution to give the corresponding sulfonyl bromide R_FSO₂Br (2a-2c) and in acetonitrile or acetic acid, to form perfluoroalkyl bromide R_FBr (3a-3c). Heating in acetonitrile at 80°C, 2a-2c were converted smoothly into 3a-3c. However, reaction of sodium α,α-dichloropolyfluoroalkanesulfinate RCCl₂SO₂Na (R?CF₃, Cl(CF₂)n, n=2, 4, 6, 5a-5d) with bromine in aqueous solution gave directly the corresponding bromoalkanes 1-bromo-1,1-dichloropolyfluoroalkane RCCl₂Br (6a-6d). In aqueous potassium iodide solution, 1a-1c, 5a and 5b also reacted with iodine to form the corresponding iodo-polyfluoroalkane 4a-4c, 7a and 7b directly. 6a and 7a underwent free radical addition to alkene readily in the presence of free radical initiator and reacted with Na₂S₂O₄ in the usual way to form α,α-dichloropolyfluoroethane sulfinate (5a). 5a was stable in strong acid, but reacted with strong base to yield 10. 5a was oxidised by hydrogen peroxide to the sulfonate 11 and reduced by zinc in dilute acid to from the α-chloro sulfinate 12.     

Unexpected formation of N-fluoroalkaneacyl anilides from the reactions of fluoroalkanesulfonyl azides with nitrobenzene and its derivatives

The thermal reactions of fluoroalkanesulfonyl azides R_fCF₂SO₂N₃1 with nitrobenzene and its derivatives XC₆H₄NO₂ (X=H, F, Cl, CF₃) gave the unexpected N-fluoroalkaneacyl anilides R_fCONHC₆H₄X (X=H, Cl, F, CF₃) in addition to fluoroalkanesulfonyl amides R_fCF₂SO₂NH₂. Under the same reaction conditions, however, nitrobenzene containing an electron-donating group RC₆H₄NO₂ (R=CH₃, OCH₃) reacted with 1 affording the corresponding N-fluoroalkanesulfonyl anilides R_fCF₂SO₂NHC₆H₃(NO₂)R. Other electron-poor benzene derivatives, such as benzaldehyde, benzoate, and acetophenone C₆H₅Y(Y=CHO, COCH₃, CO₂CH₃) all gave the meta-substituted N-fluoroalkanesulfonyl anilides R_fCF₂SO₂NHC₆H₄Y.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.