Synthesis and characterization of perhalophenyltin derivatives. Study of their reactivity toward phosphine gold(I) chlorides

The (perhalophenyl)tin derivatives [SnR₄] (1-3) and [SnR₃Cl] (4-6) (R = C₆F₅, C₆F₃Cl₂, C₆Cl₅) were prepared from SnCl₄ and LiR or [SnR₄] in the appropriate molar ratio, while the dinuclear complexes [SnR₃]₂ (7-9) were obtained by treatment of [SnR₃Cl] with potassium under toluene reflux. Complexes 2, 6·0.5toluene and 7 were structurally characterized, the latter displaying a Sn-Sn bond of 2.808(7) Å, which indicates a strong tin-tin bond with covalent character in solid state. The hexaaryldistannanes 7-9 undergo transmetallation reactions with gold(I) derivatives, such as [AuCl(PPh₃)] or [(AuCl)₂(μ-dppm)], affording the neutral species [AuR(PPh₃)] (10-12) or [(AuR)₂(μ-dppm)] (13-15) or the ionic product [Au₃Cl₂(μ-dppm)₂][Sn(C₆F₅)₃Cl₂] (16). The crystal structures of 14·CH₂Cl₂, 15 and 16·2CH₂Cl₂ were determined by X-ray diffraction, the latter showing a Au₃ nearly equilateral triangular core in the cation with gold-gold contacts of 3.128(7) and 3.227(12) Å. The main difference between the molecular structures of 14·CH₂Cl₂ and 15 (both of them displaying intramolecular gold-gold contacts of 3.142(6) and 3.160(4) Å, respectively) is the presence of an intermolecular Au?Au interaction of 3.2126(8) Å in the case of the C₆F₃Cl₂ complex that gives rise to a tetranuclear unit.     

Reactions of bis(alkynyl)silanes with HB(C6F5)2: Formation of boryl-substituted silacyclobutene derivatives

Treatment of R₂Si(CC-SiMe₃)₂ [1a (Me), 1b (Ph)] with HB(C₆F₅)₂ at low temperature (253 K (a), 273 K (b)) gives the -B(C₆F₅)₂ substituted silacyclobutene products (4a,b) under kinetic control. Upon warming to room temperature they disappear to form the thermodynamically favoured isomeric silole derivatives (2a,b). Similar treatment of Me₂Si(CC-R¹)₂ [5a (R¹ = Ph), 5b (R¹ = tert-butyl) with HB(C₆F₅)₂ at room temperature gave the stable -B(C₆F₅)₂ substituted silacyclobutene derivatives 6 and 7, respectively. Subsequent photolysis resulted in a Z- to E-isomerization of the substituted exocyclic CC double bonds in these products. The silacyclobutene derivative E-6 was characterized by an X-ray crystal structure analysis.     

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.     

(R,R,R)-Tris(2-hydroxy-1-methylethyl)- and (S,S,S)-tris(2-hydroxy-2-methylethyl)phosphine: water-soluble chiral trialkylphosphines with C3-symmetry

The first α- and β-chiral water-soluble trialkylmonophosphines, 1 and 2, respectively, both with C₃ symmetry, were synthesised from sodium phosphide and chiral mesylates, accessible from (S)-ethyl lactate. X-ray structures of a corresponding 2:1 gold(I) complex [1₂Au(I)]OTf and of a borane complex 2·BH₃ were determined.     

Synthesis, characterization and bromination of bis(phosphinoferrocenyl) gold(I) compounds

Reaction of [(dppf)Au₂Br₂] (3) {dppf = 1,1′-bis(diphenylphosphino)ferrocene} and [(dippf)Au₂Br₂] (4) {dippf = 1,1′-bis(diisopropylphosphino)ferrocene} with excess bromine yields two new complexes [(C₅H₄Br₃)(PR₂)AuBr] (R = Ph, 5; R = i-Pr, 6). Bromination of the free diphosphinoferrocene ligands produces the expected brominated cyclopentenes (C₅H₄Br₃)(PR₂) (R = Ph, 7; R = i-Pr, 8) in good yields; however, these compounds could not be complexed to gold due to reduced basicity of 7 and 8. When the bromination is performed under wet aerobic conditions the oxidized pseudo-centrosymmetric product, [doppf][FeBr₄] (9) {doppf = 1,1′-bis(oxodiphenylphosphino)ferrocene, is formed as the major product. Solid-state structures of 1, 2, 4, 6, and 9 have been established by means of single-crystal X-ray crystallography.     

Synthesis and structural characterization of diorganotin(IV) esters of salicylidene-amino acids

Eight diorganotin esters of salicylidene-L-tryptophan(Sal-T) and salicylidene-L-valine(Sal-V), [(n-Bu)₂Sn(Sal-T)] (1), [(n-Bu)₂Sn(Sal-V)] (2), [Ph₂Sn(Sal-T)] (3), [Ph₂Sn(Sal-V)] (4), [(PhCH₂)₂Sn(Sal-T)] (5), [(PhCH₂)₂Sn(Sal-V)] (6), [(4-ClC₆H₄CH₂)₂Sn(Sal-T)] (7) and [(4-ClC₆H₄CH₂)₂Sn(Sal-V)] (8) have been synthesized and characterized by elemental analysis, IR and ¹H NMR. The crystal structures of compounds 1 and 2 have been determined by X-ray single crystal diffraction. Their structures show the tin atoms of two compounds are rendered five-coordinated in distorted trigonal bipyramidal geometries.     

1-Methyl-4-ferrocenylmethyl-3,5-diphenylpyrazole: A versatile ligand for palladium(II) and platinum(II)

The syntheses and characterization of two novel ferrocene derivatives containing 3,5-diphenylpyrazole units of general formula [1-R-3,5-Ph₂-(C₃N₂)-CH₂-Fc] {Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄) and R = H (2) or Me (3)} together with a study of their reactivity with palladium(II) and platinum(II) salts or complexes under different experimental conditions is described. These studies have allowed us to isolate and characterize trans-[Pd{1-Me-3,5-Ph₂-(C₃N₂)-CH₂-Fc]}₂Cl₂] (4a) and three different types of heterodimetallic complexes: cis-[M{1-Me-3,5-Ph₂-(C₃N₂)-CH₂-Fc]}Cl₂(dmso)] {M = Pd (5a) or Pt (5b)}, the cyclometallated products [M{κ²-C,N-[3-(C₆H₄)-1-Me-5-Ph-(C₃N₂)]-CH₂-Fc}Cl(L)] with L = PPh₃ and M = Pd (6a) or Pt (6b) or L = dmso and M = Pt (8b) and the trans-isomer of [Pt{1-Me-3,5-Ph₂-(C₃N₂)-CH₂-Fc]}Cl₂(dmso)] (7b). In compounds 4a, 5a, 5b and 7b, the ligand behaves as a neutral N-donor group; while in 6a, 6b and 8b it acts as a bidentate [C(sp²,phenyl),N(pyrazole)]⁻ group. A comparative study of the spectroscopic properties of the compounds, based on NMR, IR and UV-Visible experiments, is also reported.     

Fluorinated tellurium(IV) azides and their precursors

The perfluoroaryl tellurolates C₆F₅TeLi (1) and 4-CF₃C₆F₄TeLi (2) were prepared. These intermediates were identified by NMR spectroscopy and may form, depending on the reaction conditions, either the corresponding ditellanes C₆F₅TeTeC₆F₅ (3) and CF₃C₆F₄TeTeC₆F₄CF₃ (4) by subsequent oxidation, or in the case of 1, a telluranthrene (C₆F₄Te)₂ (5) by reaction with itself. The halogenation products of 5, ( C₆F₄Te)₂F₄ (6), (C₆F₄Te)₂Cl₄ (7), (C₆F₄Te)₂Br₄ (8), as well as the azidation product (C₆F₄Te)₂(N₃)₄ (9) were synthesized. Furthermore, in pursuit of our recent work on tellurium azides, the syntheses and properties of R₂Te(N₃)₂ (R=CF₃ (10), C₆F₂H₃ (11)) and RTe(N₃)₃ (R=CF₃ (12) and C₆F₅ (13)) are reported. The crystal structures of CF₃C₆F₄TeTeC₆F₄CF₃ (4), (C₆F₄Te)₂Br₄ (8), and (C₆F₂H₃)₂Te(N₃)₂ (11) were determined.     

Structural diversity of indium complexes containing a tetradentate (OSSO)-type bis(phenolate) ligand

Indium bis(phenolato) complexes [{In(CH₃)₂(THF)}₂(L)] (L = 1,4-dithiabutanediylbis(4,6-di-tert-butylphenolato) (etbbp), 2) and [In(cytp)(CH₃)]₂ (L = (1,2-cyclohexanediyldithio)-2,2′-diphenolato (rac-cytp), 3) were prepared from [In(CH₃)₃] and the tetradentate 1,2-dithiaalkanediyl-bridged bis(phenol) LH₂. The nature of the ligand bridging two indium centers was shown by X-ray diffraction studies of the complex [{In(CH₃)₂(THF)}₂(etbbp)] (2) that was synthesized from complex [In(etbbp)(CH₃)(THF)_n] (1) by reaction with a second equivalent of [In(CH₃)₃]. A related ligand without bulky substituents on the aromatic rings leads to the dimeric compound [In(cytp)(CH₃)]₂ (3) with distorted octahedral configuration in the solid state. It was converted into the cation [In(cytp)]⁺ by methyl abstraction with [B(C₆F₅)₃].     

Synthesis,crystal structure and reactivity of a new pentacoordinated chiral dioxomolybdenum(VI) complex

The novel tridentate chiral ligand 2,6-bis{[(1R,2S,4R)-2-hydroxy-1,3,3-trimethyl-bicyclo[2.2.1]hept-2-yl]}pyridine (1) was readily prepared by reaction of 2,6-dilithiopyridine with (R)-(−)-fenchone. Reaction of 1 with [MoO₂(acac)₂] resulted in the formation of the new metal-oxo five-coordinated complex [MoO₂(ONO)] (2) [ONO = (1 – 2H)]. The reactivity of 2 has been studied and the derivatives [MoS₂(ONO)] (3) and [MoO(O₂)(ONO)] (4) were prepared. The compounds 1–4 have been characterised by ¹H and ¹³C{¹H} NMR, microanalysis and IR spectroscopy. Furthermore, the molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction. The behaviour of 2 as catalyst in oxotransfer and in nucleophilic substitution of propargylic alcohols reactions has been tested.     

Syntheses and structures of N-polyfluorophenyl- and N,N′-bis(polyfluorophenyl)ethane-1,2-diaminato(1- or 2-)platinum(II) complexes

The reaction of [PtX₂(L)] (X = Cl, Br, I; L = NH₂CH₂CH₂NY₂; Y = Et, Me) with thallium(I) carbonate and a polyfluorobenzene (RF) in pyridine (py) yields the platinum(II) complexes, [Pt{N(R)CH₂CH₂NY₂}X(py)] (R = C₆F₅, 4-HC₆F₄, 4-BrC₆F₄, or 4-IC₆F₄, Y = Et (1), Me (2), X = Cl, Br or I) in an improved synthesis. From the reaction of [PtCl₂(H₂NCH₂)₂)] with Tl₂CO₃ and 1,2,3,4-tetrafluorobenzene or 2-bromo-1,3,4,5-tetrafluorobenzene in py, the new complexes [Pt(NRCH₂)₂(py)₂] (3) (R = C₆H₂F₃-2,3,6 and C₆HBrF₃-2,3,5,6) have been isolated but the latter preparation also gave product(s) with a 4-bromo-2,3,5-trifluorophenyl group. From an analogous preparation in 4-ethylpyridine (etpy), [Pt(N(4-HC₆F₄)CH₂)₂(etpy)₂] (4) was obtained. The X-ray crystal structures of (3) (R = C₆HBrF₃-2,3,5,6) and (4) were determined as well as that of the previously prepared (3) (R = 4-BrC₆F₄) and a more precise structure of (3) (R = 4-HC₆F₄) has been obtained.     

Self-assembly of triorganotin(IV) or diorganotin(IV) moieties and 2-methylpyrazine-5-acid: Syntheses, characterizations and crystal structures of monomeric, polymeric or tetranuclear macrocyclic compounds

A series of diorganotin(IV) and triorganotin(IV) compounds of the type [R₂Sn(pca)₂ClSnR₃]₂ (RPhCH₂1, 2-ClC₆H₄CH₂2, 2-FC₆H₄CH₂3, 4-FC₆H₄CH₂4, 4-CNC₆H₄CH₂5, 4-ClC₆H₄CH₂6, 2,4-Cl₂C₆H₃CH₂7; Hpca2-methylpyrazine-5-acid), [(ⁿBu)₃Sn(pca)]_∞8, [(CH₃)₂Cl₂Sn(pca)Sn(CH₃)₂(pca)]_∞9, {[(ⁿBu)₂Sn(pca)]₂O}₂10 and {[Ph₂Sn(pca)]₃O₂[Ph₂Sn(OCH₃)]} 11 have been obtained by reactions of 2-methylpyrazine-5-acid with triorganotin(IV) chloride, diorganotin(IV) dichloride, and diorganotin(IV) oxide. All compounds were characterized by elemental, IR, and NMR spectra analyses. The crystal structure of compounds 1, 8-11 were determined by X-ray single crystal diffraction, which revealed that compound 1 was tetranuclear macrocyclic structures with seven-coordinate and five-coordinate tin atoms, compounds 8 and 9 were polymeric chain structures with five-coordinate and seven-coordinate tin atoms, compounds 10 and 11 were monomeric structures with six-coordinate and five-coordinate tin atoms.     

Palladium(II) complexes containing a bulky pyridinyl N-heterocyclic carbene ligand: Preparation and reactivity

Coordination chemistry of a pyridine imidazole-2-ylidene ligand (pyN ˆC) with sterically hindered substituents toward palladium(II) metal ions has been investigated. The palladium carbene complex [(C-pyN ˆC)Pd(η³-allyl)Cl] (3) is prepared via the transmetallation from the corresponding silver carbene complexes with [ClPd(η³-allyl)]₂. Upon the abstraction of chloride, coordination of pyridinyl-nitrogen becomes feasible to form [C,N-(pyN ˆC)Pd(η³-allyl)](BF₄) (4). Ligand substitution reaction of 4 with triphenylphosphine results in the formation of [(C-pyN ˆC)Pd(PPh₃)(η³-allyl)](BF₄)], which the pyridinyl-nitrogen donor is substituted by the phosphine. This palladium complex appears to be base sensitive. Treatment of 4 with t-butoxide causes the decomposition to yield the metal nano-particles. Furthermore, de-complexation of 4 takes place under hydrogen atmosphere to generate the carbene precursor, 1-(6-mesityl-2-picolyl)-3-mesitylimidazolium salt. Nevertheless, the palladium complex 4 shows good catalytic activity on the Suzuki-Miyaura and Mizoroki-Heck reactions.     

Coordination polymers and supramolecular structures in Ag(I)triflate-dppf systems (dppf=1,1-bis(diphenylphosphino)ferrocene)

The interaction of silver triflate (OTf⁻=SO₃(CF₃)⁻) and dppf [(C₅H₄PPh₂)₂Fe)] gave different complexes, depending on the stoichiometric proportions and reaction conditions. Under limiting dppf conditions, three different forms (1-3) of [Ag₂(OTf)₂(dppf)]_x were isolated. Single crystal X-ray diffraction analyses showed that the structure of 1 (x=2n) consists of a 2-D polymer comprising a tetra-silver basic unit, while that of 2 (x=2) possesses a discrete tetra-silver framework and that of 3 (x=n) is a linear polymer based on a di-silver repeating unit. The structures are supported by bridging dppf ligands and triflate groups. The crystal lattices of the compounds are stabilized by extensive intermolecular C-H?X hydrogen bonding (H=ring proton of Cp or Ph of dppf; X=O or F of OTf). [Ag(dppf)(OTf)] (4) and the structurally characterized mononuclear [Ag(dppf)₂](OTf) (5) were the sole products obtained from treatment of AgOTf with dppf in molar ratios of 1:1 and 1:2, respectively.     

Chronoamperometric study and X-ray analysis of Ru(II)-pdto (1,8-bis-(2-pyridyl)-3,6-dithiaoctane) complexes with substituted 1,10-phenanthrolines

This work presents cyclic voltammetry and double potential step chronoamperometry experiments corresponding to the electrochemical reduction of the substituted 1,10-phenanthroline ligands in the coordination compounds [Ru(pdto)(1,10-phenanthroline)]Cl₂ (1), [Ru(pdto)(5,6-dimethyl-1,10-phenanthroline)]Cl₂ (2), [Ru(pdto)(4,7-diphenyl-1,10-phenanthroline)]Cl₂ (3), [Ru(pdto)(4,7-dimethyl-1,10-phenanthroline)]Cl₂ (4) and [Ru(pdto)(3,4,7,8-tetramethyl-1,10-phenanthroline)]Cl₂ (5). These studies were performed in order to evaluate the stability of the electrogenerated chemical species. An EC_i mechanism for all the complexes was proposed and the rate constant value (k₁) for the chemical coupled reaction was estimated. The stability is discussed in terms of the rate constant value (k₁) and the π*-acceptor properties.     

Synthesis, characterization and reactivity of the molybdenum(VI) complex [MoCl(NAr)2(CH2CMe2Ph)] (Ar=2,6-Pr2C6H3)

The compounds [MoCl(NAr)₂R] (R=CH₂CMe₂Ph (1) or CH₂CMe₃(2); Ar=2,6-Prⁱ₂C₆H₃) have been prepared from [MoCl₂(NAr)₂(dme)] (dme=1,2-dimethoxyethane) and one equivalent of the respective Grignard reagent RMgCl in diethyl ether. Similarly, the mixed-imido complex [MoCl₂(NAr)(NBu^t)(dme)] affords [MoCl(NAr)(NBu^t)(CH₂CMe₂Ph)] (3). Chloride substitution reactions of 1 with the appropriate lithium reagents afford the compounds [MoCp(NAr)₂(CH₂CMe₂Ph)] (4) (Cp=cyclopentadienyl), [MoInd(NAr)₂(CH₂CMe₂Ph)] (5) (Ind=Indenyl), [Mo(OBu^t)(NAr)₂(CH₂CMe ₂Ph)] (6), [MoMe(NAr)₂(CH₂CMe₂Ph)] (7), [MoMe(PMe₃)(NAr)₂(CH₂CMe ₂Ph)] (8) (formed in the presence of PMe₃) and [Mo(NHAr)(NAr)₂(CH₂CMe₂P h)](9). In the latter case, a by-product {[Mo(NAr)₂(CH₂CMe₂Ph) ]₂(μ-O)}(10) has also been isolated. The crystal structures of 1, 4, 5 and 10 have been determined. All possess distorted tetrahedral metal centres with cis near-linear arylimido ligands; in each case (except 5, for which the evidence is unclear) there are α-agostic interactions present.     

The preparation, properties and X-ray structures of gold(I) trithiophosphite complexes

The first gold(I) trithiophosphite complexes were synthesised and fully characterised. Reaction of (tht)AuX (X = Cl, C₆F₅; tht = tetrahydrothiophene) with trithiophosphites (RS)₃P (R = Me, Ph) and the bicyclic [(SCH₂CH₂S)PSCH₂]₂ (²L) afforded the corresponding molecular complexes (RS)₃PAuX [R = Me, X = Cl (1); R = Me, X = C₆F₅ (2); R = Ph, X = Cl (3); R = Ph, X = C₆F₅ (4)], and ²L(AuX)₂ [X = Cl (5), X = C₆F₅ (6)]. Reacting (tht)AuCl consecutively with two mole equivalents of (MeS)₃P and then AgOTf, gave the ionic compound {[(MeS)₃P]₂Au}OTf (7). The compounds were characterised by multinuclear NMR spectroscopy, IR measurements and mass spectrometry, and the crystal and molecular structures of 1, 3, 6, two polymorphs of 2 as well as the known (MeO)₃PAuCl (8) were determined by X-ray diffraction. The halide complexes 1 and 8 are isostructural and exhibit infinite chains of “crossed-sword”-type aurophilic interactions with Au?Au contact distances of 3.2942(3) and 3.1635(4) Å, respectively. Complex 6 exhibits a long Au?Au contact of 3.4671(9) Å. Au?S interactions between 3.3455(7) and 3.520(2) Å are present in the structures of 1 and one polymorph of 2.     

Preparation of chelate bis(imine)nickel allyl systems by reaction of their corresponding butadiene complexes with electrophiles

The chelate 1,2-bis(imine)nickel(butadiene) complex 4a (chelate ligand derived from condensation of biacetyl with 2,6-diisopropylaniline) adds the strong Lewis acid B(C₆F₅)₃ at the terminal carbon atom of the butadiene ligand to yield the dipolar substituted π-allyl-type betaine complex (lig)Ni[η³-C₃H₄-CH₂B(C₆F₅)₃] (Z-6a). At 90 °C the kinetically formed product equilibrated with its E-6a isomer. Similarly, 4a adds the boron Lewis acid (pyrrolyl)B(C₆F₅)₂ to yield the corresponding neutral dipolar π-allyl betaine complex Z-7a, that slowly equilibrated with E-7a over several hours at ambient temperature. Protonation of the butadiene ligand of complex 4a was achieved by treatment with the neutral Brønsted acid (2H-pyrrol)B(C₆F₅)₃ to yield the [(lig)Ni(η³-crotyl)⁺][(pyrrolyl)B(C₆F₅)₃⁻] salt 9a (Z-/E-9a ratio=90:10 upon preparation). At 298 K this salt rearranged to a 5:95 mixture of Z-9a/E-9a with a Gibbs activation energy of ΔG^‡ (298 K)=22.3±0.2 kcal mol⁻¹. Complex 4a added [Ph₃C⁺] to the butadiene ligand to yield the salt [(lig)Ni(η³-C₃H₄-CH₂CPh₃)⁺][B(C₆F₅)₄⁻] (Z-12a), that proved isomerically stable under the applied reaction conditions. Similar reactions were carried out starting from the acenaphthylene 1,2-dione derived chelate bis(imine)Ni(butadiene) complex 4b. The systems 6, 7, 9 and 12 were found to be active ethene polymerization catalysts in the presence of Al(i-Bu)₃.     

X-ray crystal structures and solution dynamics of sodium organofluorotitanates [Na{Ti2(C5Me5)2F7}] and [NaTi6(C5Me5)5F20(H2O)]·(THF)

[Na{Ti₂(C₅Me₅)₂F₇}] (1) was prepared from sodium fluoride and [{Ti(C₅Me₅)F₃}₂] [H.W. Roesky, et al., Angew. Chem. Int. Ed. Engl. 31 (1992) 864-866]. The solid-state 1 consists of a polymeric chain of two rows of dititanate anions [Ti₂(C₅Me₅)₂F₇]⁻ connected by sodium ions in the middle of the chain. Each sodium ion is coordinated by five fluorine atoms from three [Ti₂(C₅Me₅)₂F₇]⁻ anions. The variable-temperature ¹⁹F NMR of CD₃CN solution of 1 revealed interconversions of monomeric species [Na(CD₃CN)_n{Ti₂(C₅Me₅)₂F₇}] (1solv) with different number of CD₃CN ligands on the sodium ion. The addition of HMPA to the CD₃CN solution of 1 allows ¹⁹F NMR observation of 1·HMPA (1a) and 1·HMPA·CD₃CN (1b) in the slow exchange. The solid-state structure of [NaTi₆(C₅Me₅)₅F₂₀(H₂O)]·(THF) (2·THF) reveals the sodium ion coordinated by four fluorine atoms from the anion [Ti₂(C₅Me₅)₂F₇]⁻ and by three fluorine atoms from the cluster [Ti₄(C₅Me₅)₃F₁₃(H₂O)].     

Intramolecular nucleophilic substitution in C6F5 moiety. The fluoride-dialkylamino exchange in decafluorodiphenlamino moiety

The reactions of [In(NEt₂)₃]₂ and Sb(NEt₂)₃ with an equimolar amount of decafluorodiphenylamine (DFDPA, LH) lead to the indium or antimony amides [(C₆F₅)₂NIn(NEt₂)₂]₂ (1) and (C₆F₅)₂NSb(NEt₂)₂ (2). Compound 2 rearranged further to give monofluoride Et₂NSb(F)[N(o-Et₂N-C₆F₄)(C₆F₅)] (3) and then difluoride F₂Sb[N(o-Et₂N-C₆F₄)₂] (4). The hydrolysis of 4 gave free ligand HN(o-Et₂N-C₆F₄)₂ (5). Closely related HN(o-Me₂N-C₆F₄)₂ (6) was prepared from the reaction of Bi(NMe₂)₃ with DFDPA. The reactions of LiN(C₆F₅)₂·THF with metal halides gave Sb[N(C₆F₅)₂]₃ (7), Me₃Sb(Br)[N(C₆F₅)₂] (8), Me₃Sb(Cl)[N(C₆F₅)₂] (9), Me₃Sb[N(C₆F₅)₂]₂ (10), [Li(THF)₂][In{N(C₆F₅)₂}₃Cl] (11). The X-ray structural investigations of 2 and 8 are presented.