Palladium(II)-dppe-arylazoimidazole complexes: Synthesis,and spectroscopic characterization

Reaction of [Pd(dppe)Cl₂/Br₂] with AgOTf in a dichloromethane medium followed by ligand addition led to [Pd(dppe)(OSO₂CF₃)₂] and then [Pd(dppe)(RaaiR)](OSO₂CF₃)₂ [RaaiR′ = p-R-C₆H₄-N=N-C₃H₂-NN-1-R′, (1–3), abbreviated as a N,N′-chelator, where N(imidazole) and N(azo) are represented by N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion, dppe = 1,2-bis-(diphenylphosphinoethane)]. ³¹P “¹H” NMR confirmed that due to the two phosphorus atom interaction in the azoimine symmetrical environment one sharp peak was formed. The ¹H NMR spectral measurements suggest that azo-imine link with lot of phenyl protons in the aromatic region. ¹³C (¹H) NMR spectrum, ¹H, ¹H COSY and ¹H, ¹³C HMQC spectrum assign the solution structure and stereo-retentive conformation in each complex.     

Darstellung und charakterisierung von verbindungen des typs (CH3)3ME(CF3)2 (M = Si,Ge, Sn; E = P,As)

Various preparative routes for the synthesis of (CH₃)₃SiP(CF₃)₂ are discussed. The most favourable method, reaction of (CH₃)₃MPH₂ with HE(CF₃)₂, provides a good yield of (CH₃)₃ME(CF₃)₂ compounds (M = Si, Ge, Sn; E = P, As). The reaction rate is dependent on M (Si < Ge <Sn) und E (P < As). The stability and reactivity of the (CH₃)₃ME(CF₃)₂ compounds are discussed. The new compounds were characterized by NMR and IR spectra and by cleavage reactions of the M-E bond. ¹H, ¹⁹F NMR and IR spectral data are reported.     

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.     

Synthesis of the cyanamide-derived bis(cyanoimido) complexes trans-[M(NCN)2(Ph2PCH2CH2PPh2)2] (M = Mo or W) and crystal structure of the molybdenum compound

Reaction of cyanamide (NCNH₂) with trans-[M(N₂)₂(dppe)₂] (M = Mo or W, dppe = PH₂PCH₂CH₂PPh₂) leads to the formation of the bis(cyanoimido) complexes trans-[M(NCN)₂(dppe)₂]. The crystal structure of trans-[Mo(NCN)₂(dppe)₂] has been determined by an X-ray diffraction study.     

NEW RUTHENIUM(II) COMPLEXES CONTAINING ORGANODISULFIDE LIGANDS

Abstract

The new complexes [CpRu(PPh₃)₂(RSSR)PF₆ R=CH₃, iso-Pr, CH₂C₆H₅ and C₆H₅ have been prepared from the reaction of CpRu(PPh₃)₂Cl with RSSR in CH₃OH in presence of NH₄Cl. This result contrasts with the oxidative additions of RSSR to CpFe(dppe)1 dppe=PPh₂ (CH₂)₂PPh₂ to give [CpFe(dppe)SR]PF₆ (C. Diaz et al., J. Organomet. Chem. 516, 59 (1996)). Huckel calculations on model fragments CpFe(PPh₃)₂ and CpRu(PPh₃)₂ suggest that the higher electron density of iron could explain the differences observed in reactivity. Possible biological implications are discussed.     

PREPARATION AND PROPERTIES OF DIAZENIDO,HYDRAZIDO(2-), AND HYDRIDO-HYDRAZIDO(2-) COMPLEXES OF TUNGSTEN. X-RAY PHOTOELECTRON SPECTROSCOPY OF DINITROGEN AND HYDRAZIDO(2-) COMPLEXES OF MOLYBDENUM AND TUNGSTEN

Abstract

Reactions of HBr with trans-[W(N₂)₂(dppe)PPh₂Me)₂] (1) (dppe = Ph₂CH₂CH₂PPh₂) result in protonation of coordinated N₂ but no formation of ammonia or hydrazine. The tungsten-containing product depends upon the reaction conditions: (i) in MeOH, the product formed is [WBr(NNH₂) (dppe)(PPh₂Me)₂]HBr₂ (2) which converts to the hydride, [WBr₂(H)(NNH₂(dppe)(PPh₂Me)](Br(3), with loss of phosphine in THF or CH₂Cl₂, (ii) in THF or CH₂Cl₂, the hydride (3) is formed directly. Reaction of 2 with Na₂CO₃ in MeOH results in the loss of HBr and the formation of the diazenido complex [WBr(NNH)(dppe)(PPh₂Me)₂] which reacts further with Na₂CO₃ in benzene under N₂ to lose HBr and form a mixture of 1 and trans-[W(N₂)(dppe)₂]. The reaction of 1 with aqueous HF forms [WF(NNH₂)(dppe)(PPh₂Me)₂]BF₄. The X-ray photoelectron spectra of trans-[M(N₂)₂ (dppe)₂], [MBr(NNH₂)(dppe)₂Br (M = Mo, W), [WCl(NNH₂)(dppe)₂]Cl, [WCl(N)(dppe)₂]Cl and [WCl(NH) (dppe)₂] are reported. In all of these complexes, nitrogen is in a highly reduced form.     

Structural and spectroscopic trends in mononuclear arylchalcogenolato-palladium(II) and -platinum(II) complexes: Crystal structures of [M(TeAr)2(dppe)] {M = palladium, platinum; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane}

A series of mononuclear [M(EAr)₂(dppe)] [M = Pd, Pt; E = Se, Te; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane] complexes has been prepared in good yields by the reactions of [MCl₂(dppe)] and corresponding ArE⁻ with a special emphasis on the aryltellurolato palladium and -platinum complexes for which the existing structural information is virtually non-existent. The complexes have crystallized in five isomorphic groups: (1) [Pd(SePh)₂(dppe)] and [Pt(SePh)₂(dppe)], (2) [Pd(TePh)₂(dppe)] and [Pt(TePh)₂(dppe)], (3) [Pd(SeTh)₂(dppe)], (4) [Pt(SeTh)₂(dppe)] and [Pd(TeTh)₂(dppe)], and (5) [Pt(TePh)₂(dppe)]. In addition, solvated [Pd(TePh)₂(dppe)] · CH₃OH and [Pd(TeTh)₂(dppe)] · 1/2CH₂Cl₂ could be isolated and structurally characterized. The metal atom in each complex exhibits an approximate square-planar coordination. The Pd-Se, Pt-Se, Pd-Te, and Pt-Te bonds span a range of 2.4350(7)-2.4828(7) Å, 2.442(1)-2.511(1) Å, 2.5871(7)-2.6704(8) Å, and 2.6053(6)-2.6594(9) Å, respectively, and the respective Pd-P and Pt-P bond distances are 2.265(2)-2.295(2) Å and 2.247(2)-2.270(2) Å. The orientation of the arylchalcogenolato ligands with respect to the M(E₂)(P₂) plane has been found to depend on the E-M-E bond angle. The NMR spectroscopic information indicates the formation of only cis-[M(EAr)₂(dppe)] complexes in solution. The trends in the ³¹P, ⁷⁷Se, ¹²⁵Te, and ¹⁹⁵Pt chemical shifts expectedly depend on the nature of metal, chalcogen, and aryl group. Each trend can be considered independently of other factors. The ⁷⁷Se or ¹²⁵Te resonances appear as second-order multiplets in case of palladium and platinum complexes, respectively. Spectral simulation has yielded all relevant coupling constants.     

Fluorinated peroxides derived from hexafluoroacetone. I. Insertion of (CF3)2CO into hydroperoxides

The new fluorinated peroxides HOC(CF₃)₂OOH, HOC(CF₃₂OOC(CF₃) ₂OH, and (CH₃) ₃COOC(CF₃) ₂OH have been prepared by the insertion of hexafluoroacetone into the OH bonds of hydrogen peroxide and t-butyl hydroperoxide. In addition, the alkali metal salts (HOC(CF₃) ₂OOM (M=Li or Na) and (CH₃) ₃COOC(CF₃) ₂ONa have been prepared by neutralization of the corresponding protonic compound with the appropriate metal hydride.The new compounds are safer (i.e., less flammable and less explosive) than analogous or similar hydrocarbon peroxides, though they are somewhat less thermally stable than the parent hydroperoxides.     

Tin Tetrachloride Adducts with Arylphosphoramidates: A Multinuclear (31P, 19F,and 119Sn) NMR Characterization in Solution

Abstract

The synthesis of octahedral complexes [SnCl₄L₂] (L = R₂NP(O)(OCH₂CF₃)(O-p-tolyl): R₂N = Me₂N (1), Et₂N (2), CH₂(CH₂CH₂)₂N (3), and O(CH₂CH₂)₂N (4), or L = R₂NP(O)(OCH₂CF₃)(O-p-PhNO₂): R₂N = Me₂N (5), Et₂N (6), and O(CH₂CH₂)₂N (7) is described. The new adducts have been characterized by multinuclear (³¹P, ¹⁹F, ¹¹⁹Sn) NMR, IR spectroscopy, and elemental analyses. The solution NMR data show the presence of a mixture of cis and trans isomers. The structure of the complexes in solution was further confirmed by ¹¹⁹Sn NMR spectra, which display a triplet for each isomer, indicating an octahedrally coordinated tin center. The effects of the nature of R and Ar substituents on the donor ability of the P=O group in the ligands R₂NP(O)(OCH₂CF₃)(OAr) were investigated on the basis of ¹¹⁹Sn NMR chemical shifts and used to classify these ligands according to their Lewis basicity.     

The chemical oxidation and electronic spectra of the complexes trans-[M(CNR)2(Ph2PCH2CH2PPh2)2] (M = Mo or W)

Oxidation of the complexes $\text{trans}$-[M(CNR)₂(dppe)₂] (A) (M = Mo or W; R = Me, Bu^t or CH₃C₆H₄-$\text{4}$; dppe = Ph₂PCH₂CH₂PPh₂) with diiodine or silver (I) salts gives the paramagnetic cations $\text{trans}$-[M(CNR)₂(dppe)₂]⁺, (M = Mo, R = CH₃C₆H₄-$\text{4}$; M = W, R = Bu^t) and $\text{trans}$-[M(CNR)₂(dppe)₂]²⁺ (M = Mo, R = Me or CH₃C₆H₄-$\text{4}$; M = W, R = Me or Bu^t). Mixtures of products are generally produced when dichlorine or dibromine are the oxidising agents, however pure salts, the seven-coordinate complex cations [MX(CNC₆H₄CH₃-$\text{4}$)₂(dppe)₂]⁺ (B, X = Cl or Br) have been isolated. A simple molecular orbital scheme is proposed for complexes (A) and used to discuss their electronic spectra and their oxidation.     

A study of the protonation and alkylation oft-butyl isocyanide intrans-[M(CNBu-t 2(Ph2PCH2CH2PPh2)2] (M = Mo or W): Formation of carbyne-type complexes and theirtrans- tocis-isomerization

Summary Treatment of complexestrans-[M(CNBu-t)₂(dppe)₂][(1) M = Mo or W, dppe = Ph₂PCH₂CH₂PPh₂] with protic acid gives a mixture of the aminocarbyne complexestrans- pluscis-[M(CNHBu-t)(CNBu-t)(dppe)₂]⁺ (2) and the hydridocompounds [MH(CNBu-t)₂(dppe)₂]⁺ (3), whereas reaction with an alkylating agent (R⁺) appears to give the dialkylaminocarbyne compounds [M(CNRBu-t)(CNBu-t)(dppe)₂]⁺ (4) also as a mixture of thetrans andcis isomers.     

Chemical,electrochemical and structural studies of some cis -dioxomolybdenum(VI) complexes of two tridentate ONS chelating ligands

Several cis-dioxomolybdenum complexes of two tridentate ONS chelating ligands H₂L¹ and H₂L² (obtained by condensation of S-benzyl and S-methyl dithiocarbazates with 2-hydroxyacetophenone) have been prepared and characterized. Complexes 1 and 2 are found to be of the form MoO₂ (CH₃OH) L¹?·?CH₃OH and MoO₂L, respectively, (where L^2–?=?dianion of H₂L¹ and H₂L²). The sixth coordination site of the complexes acts as a binding site for various neutral monodentate Lewis bases, B, forming complexes 3–10 of the type MoO₂LB (where B?=?γ-picoline, imidazole, thiophene, THF). The complexes were characterized by elemental analyses, various spectroscopic techniques, (UV-Vis, IR and ¹H NMR), measurement of magnetic susceptibility at room temperature, molar conductivity in solution and by cyclic voltammetry. Two of the complexes MoO₂(CH₃OH) L¹?·?CH₃OH (1) and MoO₂L¹(imz) (5) were structurally characterized by single crystal X-ray diffraction. Oxo abstruction reactions of 1 and 5 led to formation of oxomolybdenum(IV) complex of the MoOL type.     

The ESR study of the structure and reactivity of α-ketoradicals, derivatives of (CF3)3CC(O)C(O)CF3

The structure and reactivity of α-ketoradicals, derivatives of (CF₃)₃CC(O)C(O)CF₃ (1), were studied by ESR spectroscopy. The photoreduction of α-diketone1 in a solution of cyclohexane in perfluorodipentyl ether results in the formation of radicals of two types, (CF₃)₃CC(2)(O(4))·C(3)(O(6)H)CF₃ (1a) and (CF₃)₃C·C(OH)C(O)CF₃ (1b) in a ∼40∶1 ratio. The degree of delocalization of the spin density in two conformers of radical1a was calculated by the MNDO/PM3 method in the UHF approximation. It was established that radicals1a and1b are capable of reversible dimerization. The rate constant of dimerization and the enthalpy of the radical—dimer equilibrium were measured for radical1a. A decrease in the rate of dimerization of radical1a upon addition of complexing solvents ((CF₃)₃COH andp-CF₃C₆H₄CF₃) was found. The influence of the solvents on the rate of dimerization was also detected for α-ketoradical (CF₃)₃CC(O)·C(OSiMe₂Ph)CF₃ (1c). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 62–67, January, 1998.     

A novel series of nickel(II)-dppe-arylazoimidazole complexes. Synthesis and spectroscopic characterization

Reaction of [Ni(dppe)Cl₂/Br₂] with AgOTf in CH₂Cl₂ medium following ligand addition leads to [Ni(dppe)(OSO₂CF₃)₂] and then [Ni(dppe)(RaaiR)](OSO₂CF₃)₂ [RaaiR′ = p–R–C₆H₄–N=N–C₃H₂–NN-1–R′,(1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion]. ³¹P{¹H}-NMR confirm that stable bis-chelated square planar Ni(II) azoimine–dppe complex formation with one sharp peaks. The ¹H NMR spectral measurements suggest azoimine link is present with lot of phenyl protons in the aromatic region. Considering all the moities there are a lot of different carbon atoms in the molecule which gives many different peaks in the ¹³C(¹H)-NMR spectrum. In the ¹H-¹H COSY spectrum in the present complexes and contour peaks in the ¹H-¹³C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive conformation in each complexes.     

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.     

Bis(diphenylphosphino)ferrocene as an intramolecular bridging ligand in N-functionally substituted 1,3-azapropanedithiolate diiron complexes: synthesis and catalysis of proton reduction

Reaction of 1,1′-bis(diphenylphosphino)ferrocene (dppf) with [μ-(SCH₂)₂NCH₂CH₂OH]Fe₂(CO)₆ (A) or [μ-(SCH₂)₂NCH₂CH₂SAc]Fe₂(CO)₆ (C) in refluxing xylene yielded an intramolecular bridging complex [μ-(SCH₂)₂NCH₂CH₂OH]Fe₂(CO)₄(μ-dppf) (1) or [μ-(SCH₂)₂NCH₂CH₂SAc]Fe₂(CO)₄(μ-dppf) (2) in moderate yield. The structures of both complexes were fully characterized by spectroscopic methods and X-ray crystallography, and the electronic structure of 2 was further investigated by UV–vis. The cyclic voltammetry was conducted and the reduction of protons from CF₃SO₃H (TfOH), HBF₄·Et₂O, or CF₃COOH (TFA) catalyzed by 2 was observed.     

über die Reaktionen von CH3OCl,CF3OCl,CF3OF und CF3OH mit dem supersauren System HF/MF5 (M = As,Sb) Darstellung und Charakterisierung von CH3OCl(H)+MF6− und CF3OCl(H)+MF6−

On the Reactions of CH₃OCl, CF₃OCl, CF₃OF, and CF₃OH with the Superacid System HF/MF₅ (M = As, Sb). Preparation and Characterization of CH₃OCl(H)⁺MF₆^? and CF₃OCl(H)⁺MF₆^? The preparation of the chlorine oxoniumsalts CH₃OCl(H)⁺MF₆^? and CF₃OCl(H)⁺MF₆^? by protonation of CH₃OCl and CF₃OCl in the superacid solution of HF/MF₅ (M = As, Sb) is described. However CF₃OF and CF₃OH have not been protonated under the same conditions. In the case of CF₃OH the formation of F₂CO · MF₅ is observed. The novel compounds are characterized by nmr- and vibrational spectroscopy.     

CF3CH(ONO)CF3: Synthesis,IR spectrum,and use as OH radical source for kinetic and mechanistic studies

The synthesis, IR spectrum, and first‐principles characterization of CF₃CH(ONO)CF₃ as well as its use as an OH radical source in kinetic and mechanistic studies are reported. CF₃CH(ONO)CF₃ exists in two conformers corresponding to rotation about the RCO? NO bond. The more prevalent trans conformer accounts for the prominent IR absorption features at frequencies (cm^?1) of 1766 (N?O stretch), 1302, 1210, and 1119 (C? F stretches), and 761 (O? N? O bend); the cis conformer contributes a number of distinct weaker features. CF₃CH(ONO)CF₃ was readily photolyzed using fluorescent blacklamps to generate CF₃C(O)CF₃ and, by implication, OH radicals in 100% yield. CF₃CH(ONO)CF₃ photolysis is a convenient source of OH radicals in the studies of the yields of CO, CO₂, HCHO, and HC(O)OH products which can be difficult to measure using more conventional OH radical sources (e.g., CH₃ONO photolysis). CF₃CH(ONO)CF₃ photolysis was used to measure k(OH + C₂H₄)/k(OH + C₃H₆) = 0.29 ± 0.01 and to establish upper limits of 16 and 6% for the molar yields of CO and HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 159–165, 2003     

Reactions of 2,2-bis(trifluoromethyl)oxirane with alcohols under phase transfer catalysis

It was demonstrated that the reaction of 2,2-bis(trifluoromethyl)oxirane (1) with variety of alcohols could be successfully carried out under phase transfer catalysis conditions using sodium or potassium hydroxide as a base. For example, reaction of CH₃OH, C₂H₅OCH₂CH₂OH, HOCH₂CH₂OH with one or two moles of 1 in the presence of the catalyst [(C₄H₉)₄N⁺HSO₄⁻] gives the corresponding tertiary alcohols R[OCH₂C(CF₃)₂OH]_n (n=1 or 2) in 43-53% yield, along with some O[CH₂C(CF₃)₂OH]₂. Benzyl alcohol and phenol under similar conditions are less active, producing in the reaction with 1 the corresponding adducts ArOCH₂C(CF₃)₂OH in 31-35% yield. Fluorinated alcohols, such as CF₃CH₂OH, ClCF₂CH₂OH, HCF₂CF₂CH₂OH have much higher reactivity towards 1 giving ring opening products in 82-97% yield. Even in the reaction of hindered hexafluoro-iso-propanol the corresponding adduct was isolated in 43% yield. Surprisingly, the reaction of iso-propanol and epoxide 1, results in the formation of O[CH₂C(CF₃)₂OH]₂ as a major product, isolated in 56% yield. Possible mechanism for the formation of the last product was proposed.     

Mono- and bimetallic platinum(II) and palladium(II) complexes containing fluorinated benzothiolates

The new mononuclear palladium(II) and platinum(II) [M(p-SC₆F₄(CF₃))₂(dppe)] complexes M = Pd 1a, Pt 2a; [M(o-SC₆H₄(CF₃))₂(dppe)] M = Pd 1d, Pt 2d as well as the previously known [M(SC₆F₅)₂(dppe)] M = Pd 1b, Pt 2b and [M(p-SC₆HF₄)₂(dppe)] M = Pd 1c, Pt 2c, have been used as metalloligands for the preparation of the heteroleptic bimetallic complexes [M₂(μ-SRf)₂(dppe)₂](SO₃CF₃)₂ M = Pd, Rf = p-C₆F₄(CF₃) 3a, C₆F₅3b, p-C₆HF₄3c, o-C₆H₄(CF₃) 3d; M = Pt, Rf = p-C₆F₄(CF₃) 4a, C₆F₅4b, p-C₆HF₄4c and o-C₆H₄(CF₃) 4d. Variable temperature ¹⁹F NMR experiments show that the fluorothiolate bridged bimetallic compounds are fluxional in solution whereas mononuclear complexes are not. The solid state X-ray diffraction structures of [Pd(p-SC₆HF₄)₂(dppe)] (1c), [Pt(SC₆F₅)₂(dppe)] (2b) and [Pt(o-SC₆H₄(CF₃))₂(dppe)] (2d) show square-planar coordination around the metal centers. The solid state molecular structure of the compound [Pt₂(μ-o-SC₆H₄(CF₃))₂(dppe)₂](SO₃CF₃)₂ (4d), exhibit a planar [Pt₂(μ-S)₂] ring with the sulfur substituents in an anti configuration.