REACTIONS OF CARBONYLSULPHIDE WITH [Rh(PPh3)3CI] AND [Pt(PPh3)3]

Abstract

Activation of small inorganic molecules (H₂, N₂, O₂, CO, NO, CO₂, SO₂, CS₂) by the complexes of transition metal ions like Rh(I), Ir(I), Pt(O) and Ru(II) have gained considerable interest during the last decade.^1–8 Because of the similarity of CO₂ and CS₂ molecules with COS, one would expect COS to form complexes with the transition metal ions analogous to those of CO₂ and CS₂. In addition, COS being susceptible to decomposition into CO and S, could also form carbonyl complexes. Until now, the only reaction of COS that has been successfully carried out is with [Pt(PPh₃)₃] which resulted in the formation of [Pt(COS)(PPh₃)₂] and [Pt₂S(CO) (PPh₃)₃]. ^8,9 It will, therefore, be interesting to study further the reactions of COS with the complexes of transition metal ions. The results of a preliminary study of such reactions with [Rh(PPh₃)₃Cl] and [Pt(PPh₃)₃] are reported in this communication.     

Strukturen von neuen Bis(pentafluorophenyl)halogenomercuraten [{Hg(C6F5)2}3(μ‐X)]— (X = Cl,Br, I)

Structures of New Bis(pentafluorophenyl)halogeno Mercurates [{Hg(C₆F₅)₂}₃(μ‐X)]^— (X = Cl, Br, I) From the reactions of [PNP]Cl or [PPh₄]Y (Y = Br, I) with Hg(C₆F₅)₂ crystals of the composition [Cat][{Hg(C₆F₅)₂}₃X] (Cat = PNP, X = Cl ( 1 ); Cat = PPh₄, X = Br ( 2 ), I ( 3 )) are formed. 1 crystallizes in the triclinic space group P1¯, 2 and 3 crystallize isotypically in the monoclinic space group C2/c. In the crystals the halide anions are surrounded by three Hg(C₆F₅)₂ molecules. The reaction of [PPh₄]Br with Hg(C₆F₅)₂ under slightly changed conditions gives the compound [PPh₄]₂[{Hg(C₆F₅)₂}₃(μ‐Br)][{Hg(C₆F₅)₂}₂(μ‐Br)] ( 4 ).     

Metallatriazadiphosphorines of zinc(II), cadmium(II) and mercury(II)

Metallatriazadiphosphorine complexes corresponding to [{N(PPh₂NR)₂}M(OAc)] and [{N(PPh₂NR)₂}₂M], (R = Ph or SiMe₃; M = Zn, Cd or Hg) have been synthesized under strictly anhydrous and inert conditions by the reaction of the acyclic bis-silylated phosphazene ligand, [HN(PPh₂NSiMe₃)₂], or the bis-phenylated phosphazene ligand, [HN(PPh₂NPh)₂], with Zn, Cd and Hg acetate in 1:1 and 2:1 molar ratios. These complexes are highly soluble in common organic solvents, but unstable hydrolytically as well as thermally, even under reduced pressure. Molecular weight determinations in benzene indicated the monomeric nature of these complexes. Further, they have been characterized on the basis of elemental analysis and spectral studies: i.r. and n.m.r. (¹H, ¹³C and ³¹P) that plausibly reveal a trigonal planar and tetrahedral geometry around the metal atom in the complexes.     

Proton Affinities of Cationic Carbone Adducts [AC(PPh3)2]+ (A=Halogen,Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh3)2]2+

This work reports the syntheses and the first crystal structures of the cationic carbone adducts [FC(PPh₃)₂]⁺ and [BrC(PPh₃)₂]⁺ and the protonated dication [FC(H)(PPh₃)₂]²⁺, which are derived from the carbone C(PPh₃)₂. Quantum chemical calculations and bonding analyses were carried out for the series of cations [AC(PPh₃)₂]⁺ and dications [AC(H)(PPh₃)₂]²⁺, where A=H, Me, F, Cl, Br, I. The bonding analysis suggests that the cations are best described as phosphane complexes L→(CA)⁺←L (L=PPh₃), which are related to the neutral borylene adducts L→(BA)←L (L=cyclic carbene; A=H, aryl) that were recently isolated. The carbone adducts [AC(PPh₃)₂]⁺ possess a π electron lone pair at carbon and they can easily be protonated to the dications [AC(H)(PPh₃)₂]²⁺. The calculations of the dications indicate that the molecules are best represented as complexes L→(CHA)²⁺←L (L=PPh₃) where a carbene dication is stabilized by the ligands. The central carbon atom in the cations and even in the dications carries a negative partial charge, which is larger than the negative charge at fluorine. There is also the peculiar situation in which the carbon–fluorine bonds in [FC(PPh₃)₂]⁺ and [FC(H)(PPh₃)₂]²⁺ exhibit the expected polarity with the negative end at fluorine, but the carbon atom has a larger negative charge than fluorine. Given the similarity of carbodiphosphorane C(PPh₃)₂ and carbodicarbene C(NHC)₂, we expect that analogous compounds [AC(NHC)₂]⁺ and [AC(H)(NHC)₂]²⁺ with similar features as [AC(PPh₃)₂]⁺ and [AC(H)(PPh₃)₂]²⁺ can be isolated.     

Synthesis and Structure of the Clusters [Hg2(μ—SePh)2(SePh)2(PPh3)2] and [Hg3Br3(μ—SePh)3] · 2 DMSO

The compounds [Hg₂(μ—SePh)₂(SePh)₂(PPh₃)₂] ( I ) and [Hg₃Br₃(μ—SePh)₃] · 2 DMSO ( II ) are formed by reactions of [Hg(SePh)₂] with PPh₃ in THF( I ) or with HgBr₂ in DMSO ( II ) at room temperature. X—ray crystallography reveals that the cluster I consists of a distorted square built by each two Hg and Se atoms. The Hg atoms have almost tetrahedral co‐ordination environments formed by selenium atoms of two (μ‐^—SePh) ligands and Se and P atoms of terminal ^—SePh and PPh₃ ligands. The compound II is a six‐membered ring with alternating Hg and Se atoms in the chair conformation. Two DMSO molecules occupy positions below and above the [Hg₃Se₃] ring with the oxygen atoms directed to the centre of the ring.     

Crystal and molecular structures of (η-xanthene)- (η-cyclopentadienyl)iron(II) hexafluorophosphate and (η-2-methylthianthrene)(η-cyclopentadienyl)iron(II) hexafluorophosphate

The neutral complexes (η⁵-C₅H₅NiXL (X = Cl, L = PPh₃ (I); L = PCy₃ (II); X = Br, L = PPh₃ (III); L = PCy₃ (IV); X = I, L = PPh₃ (V); L = PCy₃ (VI)) have been obtained by treating NiX₂L₂ with thallium cyclopentadienide. The same reaction in the presence of TlBF₄ gives cationic derivatives [(η⁵-C₅H₅)NiL₂]BF₄ (L = 2PPh₂Me (VII); L = dppe (VIII)), whereas mononuclear complexes containing two different ligands (L₂ = PPh₃ + PCy₃ (IX)) or dinuclear [(η⁵-C₅H₅)Ni(PPh₃)]₂dppe(BF₄)₂ (X) are obtained from the reaction of III with TlBF₄ in the presence of a different ligand. Reduction of cationic complexes with Na/Hg gives very unstable nickel(I) derivatives (η⁵-C₅H₅)NiL₂, which could not be isolated purely. Similar reduction of neutral complexes under CO gives a mixture of decomposition products containing [(η⁵-C₅H₅)Ni(CO)]₂ and nickel(o) carbonyls, whereas in the presence of acetylenes, dinuclear [(η⁵-C₅H₅)Ni]₂(RCCR′) (R = R′ = Ph; R = Ph, R′ = H) are obtained.     

Addition von kationischen Lewis‐Säuren [M′Ln]+ (M′Ln = Fe(CO)2Cp,Fe(CO)(PPh3)Cp,Ru(PPh3)2Cp,Re(CO)5, ${1 \over 2}$ Pt(PPh3)2, W(CO)3Cp an die anionischen Thiocarbonyl‐Komplexe [HB(pz)3(OC)2M(CS)]− (M = Mo,W; pz = 3,5‐dimethylpyrazol‐1‐yl)

Addition of Cationic Lewis Acids [M′L_n]⁺ (M′L_n = Fe(CO)₂Cp, Fe(CO)(PPh₃)Cp, Ru(PPh₃)₂Cp, Re(CO)₅, Pt(PPh₃)₂, W(CO)₃Cp to the Anionic Thiocarbonyl Complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)₂Cp]⁺, [Fe(CO)(PPh₃)Cp]⁺, [Ru(PPh₃)₂Cp]⁺, [Re(CO)₅]⁺, [ Pt(PPh₃)₂]⁺, [W(CO)₃Cp]⁺ and the anionic thiocarbonyl complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)₃(OC)₂MCSM′L_n].     

Carbonylvanadium complexes of the tripod ligands MeC(CH2PPh2)3 and P(CH2CH2PPh2)3

UV irradiation of [Et₄N] [V(CO)₆] in the presence of the tripod ligands (L) MeC(CH₂PPh₂)₃ (cp₃) and P(CH₂CH₂PPh₂)₃ (pp₃) yields [Et₄N] [V(CO)₅L], cis-[Et₄N] [V(CO)₄L] and mer-[Et₄N] [V(CO)₃L] (where the meridional configuration for L = cp₃ is uncertain). Except for [Et₄N] [V(CO)₅cp₃], all these species were isolated. The complexes are characterized by their IR, ³¹P and ⁵¹V NMR spectra.     

Metal catalysed Brooke rearrangement of 3-Halo-1-(trimethylsilyl) propan-2-one (Halo = Cl or Br)

The complexes [IrH(CO)(PPh₃)₃], trans-[IrCI(CO)- (PPh₃)₂], [RhH(PPh₃)₄], [Pd(PPh₃)₄], [Pt(trans-stilbene)(PPh₃)₂] and [Pt(η³-CH₂-COCH₂)-(PPh₃)₂] catalyse the rearrangement of Me₃SiCH₂C(O)CH₂Cl to CH₂?C(OSiMe₃)-CH₂Cl.     

Preparation and Reactivity of Mixed‐Ligands Hydride Complexes [RuHCl(CO)(PPh3)2{P(OR)3}]

Mixed‐ligands hydride complexes [RuHCl(CO)(PPh₃)₂{P(OR)₃}] ( 2 ) (R = Me, Et) were prepared by allowing [RuHCl(CO)(PPh₃)₃] ( 1 ) to react with an excess of phosphites P(OR)₃ in refluxing benzene. Treatment of hydrides 2 first with triflic acid and next with an excess of hydrazine afforded hydrazine complexes [RuCl(CO)(κ¹‐NH₂NHR1)(PPh₃)₂{P(OR)₃}]BPh₄ ( 3 , 4 ) (R1 = H, CH₃). Diethylcyanamide derivatives [RuCl(CO)(N≡CNEt₂)(PPh₃)₂{P(OR)₃}]BPh₄ ( 5 ) were also prepared by reacting 2 first with HOTf and then with N≡CNEt₂. The complexes were characterized spectroscopically and by X‐ray crystal structure determination of [RuHCl(CO)(PPh₃)₂{P(OEt)₃}] ( 2b ).     

Univalent Gallium and Indium Phosphane Complexes: From Pyramidal M(PPh3)3+ to Carbene‐Analogous Bent M(PtBu3)2+ (M=Ga,In) Complexes

In a new oxidative route, Ag⁺[Al(OR^F)₄]^? (R^F=C(CF₃)₃) and metallic indium were sonicated in aromatic solvents, such as fluorobenzene (PhF), to give a precipitate of silver metal and highly soluble [In(PhF)_n]⁺ salts (n=2, 3) with the weakly coordinating [Al(OR^F)₄]^? anion in quantitative yield. The In⁺ salt and the known analogous Ga⁺[Al(OR^F)₄]^? were used to synthesize a series of homoleptic PR₃ phosphane complexes [M(PR₃)_n]⁺, that is, the weakly PPh₃‐bridged [(Ph₃P)₃In–(PPh₃)–In(PPh₃)₃]²⁺ that essentially contains two independent [In(PPh₃)₃]⁺ cations or, with increasing bulk of the phosphane, the carbene‐analogous [M(PtBu₃)₂]⁺ (M=Ga, In) cations. The M^I? P distances are 27 to 29 pm longer for indium, and thus considerably longer than the difference between their tabulated radii (18 pm). The structure, formation, and frontier orbitals of these complexes were investigated by calculations at the BP86/SV(P), B3LYP/def2‐TZVPP, MP2/def2‐TZVPP, and SCS‐MP2/def2‐TZVPP levels.     

Gemischtligandkomplexe des Nickel(0) und Kobalt(I) mit anionischen Liganden des Typs E(C6H5)3− (E  Ge,Sn, Pb)

Mixed Ligand Complexes of Nickel(0) and Cobalt(I) with the Anionic Ligands E(C₆H₅)₃^? (E ? Ge, Sn, Pb) Complexes of the general formula M^INi(PPh₃)₃(EPh₃)(THF)_x (E ? Ge[Ia], Sn[Ib], Pb[Ic]) and M^I₃Ni(PPh₃)(EPh₃)₃(THF)_x (E ? Ge[IIa], Sn[IIb]) are formed from (Ph₃P)₂Ni(C₂H₄) by substitution with M^IEPh₃. The analogous complexes of the ligand SiPh₃^? could not be prepared, because of the formation of SiPh₄ from LiSiPh₃ and coordinated PPh₃. Attempts to synthesize a nickel(II) complex of the ligand SnPh₃^? had no success, only possible decomposition products of these compounds, like (nBu₂PPh)₂Ni^II(Ph)Cl and Na_xNi°(PPh₃)_4?x(SnP₄)_x(THF)_Y, were isolated. NaCo^I(PPh₃)₂(SnPh₃)₂(THF)₇ (IV) was prepared by the reaction of Co(PPh₃)₃Cl and NaSnPh₃. ¹H-NMR and ¹¹⁹Sn Mössbauer spectra show a higher donor action of SnPh₃^? in IIb than in Ib. This causes a stronger π-back donation Ni → P in the case of IIb. IV is a paramagnetic compound, the vis-spectrum is discussed using simple crystal field theory.     

Synthesis and characterization of cyclometallated palladium(II) and platinum(II) complexes with amide-thiolate ligands

The redox reaction of bis(2-benzamidophenyl) disulfide (H₂L-LH₂) with [Pd(PPh₃)₄] in a 1:1 ratio gave mononuclear and dinuclear palladium(II) complexes with 2-benzamidobenzenethiolate (H₂L⁻), [Pd(H₂L-S)₂(PPh₃)₂] (1) and [Pd₂(H₂L-S)₂ (μ-H₂L-S)₂(PPh₃)₂] (2). A similar reaction with [Pt(PPh₃)₄] produced only the corresponding mononuclear platinum(II) complex, [Pt(H₂L-S)₂(PPh₃)₂] (3). Treatment of these complexes with KOH led to the formation of cyclometallated palladium(II) and platinum(II) complexes, [Pd(L-C,N,S)(PPh₃)]⁻ ([4]⁻) and [Pt(L-C,N,S) (PPh₃)]⁻ ([5]⁻). The molecular structures of 2, 3 and [4]⁻ were determined by X-ray crystallography.     

Azidokomplexe von Mangan(II) und Cobalt(II) Die Kristallstrukturen von (PPh4)2[Mn(N3)4] und (PPh4)2[Co(N3)3Cl]

Azido Complexes of Manganese(II) and Cobalt(II). Crystal Structures of (PPh₄)₂[Mn(N₃)₄] and PPh₄₂[Co(N₃)₃Cl] (PPh₄)₂[Mn(N₃)₄] and (PPh₄)₂[Co(N₃)₃Cl] were obtained as light-brown and green blue, nonexplosive crystalline compounds, respectively. They are only slightly sensitive to moisture and were obtained from the tetrachloro complexes (PPh₄)₂MCl₄ by reactions with silver azide in dichloromethane. The compounds were characterized by thier i.r. spectra and by crystal structure analyses. Both crystallized in the monoclinic space group C2/c, Z = 4, but they are not isotypic. (PPh₄)₂[Mn(N₃)₄]: structure determination with 711 independent reflexions, R = 0.097; a = 2249.1, b = 1499.6, c = 1370.3 pm, β = 104.86°. (PPh₄)₂[Co(N₃)Cl]: 2753 reflexions, R = 0.075; a = 1119.7, b = 1899.2, c = 2115.4 pm, β = 90.47°. The structures consist of PPh₄⁺ ions and of anions that are situated on twofold crystallographic rotation axes. The anions show positional disorder, statistically assuming two different orientations with probabilities of 50% each; in the case of [Co(N₃)₃Cl]^2?, the Cl atom is superimposed statistically with an azido group, whereas the [Mn(N₃)₄]^2? ion is tilted by about 20° from the ideal position to two sides of the crystallographic axis. In both compounds the cation form layers and the anions are located between the layers.     

Chelate structures of 5-(H/Br)-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazones (H2L): Synthesis and structural characterizations of [Ni(L)(PPh3)] and [Ru(HL)2(PPh3)2]

The reactions of 5-R-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazone {R: H (L¹); Br (L²)} with [M^II(PPh₃)nCl₂] (M = Ni, n = 2 and M = Ru, n = 3) in a 1:1 molar ratio have given stable solid complexes corresponding to the general formula [Ni(L)(PPh₃)] and [Ru(HL)₂(PPh₃)₂]. While the 1:1 nickel complexes are formed from an ONS donor set of the thiosemicarbazone and the P atom of triphenylphosphine in a square planar structure, the 1:2 ruthenium complexes consist of a couple from each of N, S and P donor atoms in a distorted octahedral geometry. These mixed-ligand complexes have been characterized by elemental analysis, IR, UV–Vis, APCI-MS, ¹H and ³¹P NMR spectroscopies. The structures of [Ni(L²)(PPh₃)] (II) and [Ru(L¹H)₂(PPh₃)₂] (III) were determined by single crystal X-ray diffraction.     

Ruthenium(II) complexes with 2-(benzylimino-methyl)-4-R-phenol containing the trans(PPh3),cis(CO,Cl)-{Ru(PPh3)2(CO)Cl} unit

Reactions of [Ru(PPh₃)₃Cl₂] with 2-(benzylimino-methyl)-4-R-phenol (H^RL, R = H, Cl, Br and OMe) in boiling methanol in presence of triethylamine afford ruthenium(II) complexes of general formula [Ru(^RL)(PPh₃)₂(CO)Cl] in 57-64% yield. Microanalysis, spectroscopic (infrared, electronic and NMR) and cyclic voltammetric measurements have been used for the characterization of the complexes. Crystal structures of two representative complexes have been determined by X-ray crystallography. The carbonyl, the chloride, the N,O-donor ^RL⁻ and the two mutually trans PPh₃ molecules assemble a distorted octahedral CClNOP₂ coordination sphere around the metal centre in each complex. The complexes display the Ru(II) → Ru(III) oxidation in the potential range 0.62-1.16 V (vs. Ag/AgCl).     

Neue Phosphido-verbrückte Mehrkernkomplexe des Ag,Cd und Zn Die Kristallstrukturen von [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] und [M4Cl4(PPh2)4(PnPr3)2] (M = Zn,Cd)

New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag₄(PPh₂)₄(PMe₃)₄], [Ag₆(PPh₂)₆(P^tBu₃)₂] and [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn, Cd) AgCl reacts with Ph₂PSiMe₃ in the presence of a tertiary Phosphine PMe₃ or P^tBu₃ to form the multinuclear complexes [Ag₄(PPh₂)₄(PMe₃)₄] ( 1 ) and [Ag₆(PPh₂)₆(P^tBu₃)₂] ( 2 ). In analogy to that MCl₂ reacts with Ph₂PSiMe₃ in the presence of PⁿPr₃ to form the two multinuclear complexes [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn ( 3 ), Cd ( 4 )). The structures were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2 : space group P–1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3 : space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4 : space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh₂)₂]_n (M = Zn, Cd).     

Synthesis,spectroscopic properties,structural characterization and electrochemistry of mixed ligand complexes of copper(I) halide with PPh3 and naphthylazoimidazole

The reaction of CuX (X = Cl, Br, I) with a mixture of PPh₃ and 1-alkyl-2-(naphthyl-α/β-azo)imidazole has synthesized mixed ligand complexes of the composition, [Cu(α/β-NaiR)(PPh₃)X]. The spectroscopic characterization (IR, UV–Vis, ¹H NMR) supports this formulation. The single crystal X-ray diffraction study of [Cu((α-NaiMe)(PPh₃)I] (7a) (α-NaiMe = 1-methyl-2-(naphthyl-α-azo)imidazole) shows a distorted tetrahedral geometry about Cu(I). Cyclic voltammograms of the complexes show a high potential Cu(II)/Cu(I) couple and azo reductions. The [Cu(α/β-NaiR)(PPh₃)I] complexes show an additional oxidative response at 0.4 V that is assigned to I/I⁻ A sharp anodic peak at ∼−0.2 V is assigned to the oxidation of metallic Cu, deposited on electrode surface upon scanning to the negative side of the SCE. DFT and TD-DFT computations of [Cu((α-NaiMe)(PPh₃)I] (7a), [Cu((α-NaiMe)(PPh₃)I]⁺ (7a⁺) and [Cu((α-NaiMe)(PPh₃)I]⁻ (7a⁻) were carried out to examine the electronic configuration and to explain the spectral and redox properties of the complexes.     

Reactions of nitrilium triflate salts with trans-[IrCl(CO)(PPh3)2

Low yields of the ionic carbene complexes [Ir(RCNHMe)Cl(CO)(PPh₃)₂-(O₃SCF₃)]O₃SCF₃]O₃SCF₃ (R  Ph or PhCH₂) have been isolated from the reactions of trans-[IrCl(CO)(PPh₃)₂] with the nitrilium triflate salts, [RCNMe]O₃SCF₃. The major products from these, and the similar reactions of the nitrilium salts where R  Me or Bu^t, are amorphous, yellow complexes [Ir(RCNHMe)Cl(CO)(PPh₃)₂O₃SCF₃.     

Synthesen und Charakterisierungen der ersten Tris‐ und Tetrakis(trifluormethyl)palladate(II) und ‐platinate(II), [M(CF3)3(PPh3)]— und [M(CF3)4]2— (M = Pd,Pt)

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.