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1.
The relative fluoride donor ability: C6F5BrF2 > C6F5IF2 > C6F5IF4 was outlined from reactions with Lewis acids of graduated strength in different solvents. Fluoride abstraction from C6F5HalF2 with BF3·NCCH3 in acetonitrile (donor solvent) led to [C6F5HalF·(NCCH3)n][BF4]. The attempted generation of [C6F5BrF]+ from C6F5BrF2 and anhydrous HF or BF3 in weakly coordinating SO2ClF gave C6F5Br besides bromoperfluorocycloalkenes C6BrF7 and 1-BrC6F9. In reactions of C6F5IF2 with SbF5 in SO2ClF the primary observed intermediate (19F NMR, below 0 °C) was the 4-iodo-1,1,2,3,5,6-hexafluorobenzenium cation, which converted into C6F5I and 1-IC6F9 at 20 °C. The reaction of C6F5IF4 with SbF5 in SO2ClF below −20 °C gave the cation [C6F5IF3]+ which decomposed at 20 °C to C6F5I, 1-iodoperfluorocyclohexene, and iodoperfluorocyclohexane. Principally, the related perfluoroalkyl compound C6F13IF4 showed a different type of products in the fast reaction with AsF5 in CCl3F (−60 °C) which resulted in C6F14. Intermediate and final products of C6F5HalFn−1 (n = 3, 5) with Lewis acids were characterized by NMR in solution. Stable solid products were isolated and analytically characterized. 相似文献
2.
The molecules ArFXeF (ArF=C6F5, 2,4,6-C6H2F3) with a more polar Xe-F bond than XeF2 are versatile starting materials for substitution reactions. Fluorine-aryl substitutions with Cd(ArF)2, C6F5SiMe3/[F]−, and C6F5SiF3 formed symmetric and/or asymmetric diarylxenon compounds. Applying C6F5BF2, with a higher F−-affinity than the corresponding aryltrifluorosilane, in contrast gave the salt [RXe] [ArFBF3]. Using the alkenyl and alkyl compounds CF2=CFSiMe3/[F]−, CF3SiMe3/[F]−, and Cd(CF3)2 in reactions with C6F5XeF, the perfluoroalkenyl or -alkyl transfer reagents were consumed without observing C6F5XeCF=CF2 or C6F5XeCF3 but the formation of Xe(C6F5)2 (dismutation product) and in the latter case C6F5CF3 (coupling product), gave hints of the desired intermediates. 相似文献
3.
Chloride abstraction from [{M(η3 --- C3H5)Cl}n] (M = Pt, n = 4 or M = Pd, n = 2) by (NBu4)2[cis-Pt(C6F5)2(CCSiMe3)2] (1) gives rise to novel homo- and hetero-dinuclear zwitterionic derivatives (NBu4) [{cis-Pt(C6F5)2(CCSiMe3)2}M(η3-C3H5)] (M = Pt 2; M = Pd 3) which are formed by a M(η3-allyl)+ unit attached to both alkynyl ligands of the {cis-Pt(C6F5)2(CCSiMe3)2}2− fragment. The structure of 3 has been established by X-ray diffraction. 相似文献
4.
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 ). 相似文献
5.
Dieter Naumann Wieland Tyrra Rudolf Herrmann Ingo Pantenburg Mathias S. Wickleder 《无机化学与普通化学杂志》2002,628(4):833-842
Te(C6F5)4 was prepared from the reactions of TeCl4 or Te(C6F5)2Cl2 with Grignard reagents or AgC6F5 in moderate to good yields. Substitution reactions with Me3SiX (X = Cl, Br, OSO2CF3), with equimolar amounts of Br2, with AgNO3 and with H[BF4] or BF3·OEt2 yielded the Te(C6F5)3X derivatives (X = Cl, Br, OSO2CF3, NO3, BF4). Oxidation reactions of Cd, Hg, and Pd0 complexes led to Te(C6F5)2 and the corresponding bis(pentafluorophenyl) derivatives M(C6F5)2 (M = Cd, Hg, Pd) and with InBr to In(C6F5)2Br. From very slow hydrolysis of Te(C6F5)4 the oxide Te(C6F5)2O was prepared. The thermal decomposition, the NMR and mass spectra of the partially new compounds are discussed. The crystal structures of Te(C6F5)3Br (monoclinic, P21/a, Z = 4), [Te(C6F5)3][OSO2CF3] (monoclinic, P21/n, Z = 16) and [Te(C6F5)2O]2 (triclinic, P1¯, Z = 2) were determined. 相似文献
6.
Rafael Usón Antonio Laguna Juan Forniés Ignacio Valenzuela Peter G. Jones George M. Sheldrick 《Journal of organometallic chemistry》1984,273(1):129-139
Reactions of PdRR′(η1-dppm)2 (R = R′= C6F5 or C6Cl5; R = C6F5, R′= Cl; dppm = Ph2PCH2PPh2) with the gold derivatives ClAu(tht), C6F5Au(tht), (C6F5)3Au(tht) or O3ClOAuPPh3 (tht = tetrahydrothiophen) in appropriate ratios yield the bi- or tri-nuclear complexes PdRR′(dppm)2AuCl, PdRR′(dppm)2Au(C6F5); PdRR′(dppm)2Au(C6F5)3; PdRR′(dppmAuCl)2; PdRR′(dppmAuC6F5)2; PdRR′[dppmAu(C6F5)3]2, [PdRR′(dppm)2Au]X (X = ClO4 or BPh4); [PPh3Au(dppm)Pd(C6F5)2(dppm)AuCl]ClO4 or [PPh3 Au(dppm)Pd(C6F5)2(dppm)Au(C6F5)3]ClO4. The structure of trans-Pd(C6F5)2[dppmAu(C6F5)]2 has been determined by X-ray diffraction. 相似文献
7.
(C6F5)2Te reacts with elemental fluorine step by step to form the tellurium fluorides (C6F5)2TeF2, (C6F5)2TeF4 and (C6F11)2TeF4, which can be isolated in pure states. The intermediates (C6F11?2n)2TeF4 (n = 1,2) are detected spectroscopically. (C6F5)2TeF2 is also formed from the reaction of (C6F5)2Te with XeF2. The preparations, properties and 19F n.m.r. spectra of these new compounds are discussed, the mass and vibrational spectra are described. 相似文献
8.
Xue-Hong Wei Peter B. Hitchcock Michael F. Lappert 《Journal of organometallic chemistry》2008,693(20):3256-3262
Five crystalline 2-(dimethylsila)pyrimidine derivatives
(Z) have been prepared in excellent 1–4 or satisfactory 5 yield and characterised. The source of each was ultimately Li[CH(SiMe2R)(SiMe2OMe)] [R = Me (B) or OMe (I)]. Compound 1 (Z with Ar = Ph, X = SiMe3, n = 1) was obtained from Z [with Ar = Ph, X = Li(OEt2), n = 4; previously isolated from B [P.B. Hitchcock, M.F. Lappert, X.-H. Wei, J. Organomet. Chem. 689 (2004) 1342]] and Me3SiCl. The potassium salt 2 [Z with Ar = C6H4But-4; X = K(thf)3, n = 2] was made from K[CH(SiMe3)(SiMe2OMe)] (C) (via B) and 4-ButC6H4CN. Treatment of 2 with 1,2-dibromoethane afforded 3 (Z with Ar = 4-ButC6H4; X = H, n = 1); which when reacted with successively n-butyllithium and Me3SiCl produced 4 (Z with Ar = 4-ButC6H4, X = SiMe3, n = 1). Compound 5 [Z with Ar = 4-ButC6H4, X = Li(hmpa)2, n = 1] resulted from I with 4-ButC6H4CN and then OP(NMe2)3 (≡ hmpa). Plausible reaction pathways from the appropriate alkali metal alkyl C or I to 2 or 5, respectively, are suggested; these involve regiospecific 1,3-migrations of SiMe2OMe from C → N and electrocyclic loss of Me3SiOMe or SiMe2(OMe)2, respectively. The X-ray structures of crystalline 1, 2 and 5 are presented. 相似文献
9.
Abby R O'Connor Chip Nataro James A Golen Arnold L Rheingold 《Journal of organometallic chemistry》2004,689(14):2411-2414
A new chemical oxidant [N(4-C6H4Br)3][B(C6F5)4], was prepared and used to synthesize [Fe(C5H5)2][B(C6F5)4]. The crystal structure of [Fe(C5H5)2][B(C6F5)4] was determined. 相似文献
10.
Alberto Fernndez Patricia Uría Jesús J. Fernndez Margarita Lpez-Torres Antonio Surez Digna Vzquez-García Ma Teresa Pereira Jos M. Vila 《Journal of organometallic chemistry》2001,620(1-2):8-19
Treatment of N-(2-chlorobenzylidene)-N,N-dimethyl-1,3-propanediamine (1) and N-(2-bromo-3,4-(MeO)2-benzylidene)-N,N-dimethyl-1,3-propanediamine (20) with tris(dibenzylideneacetone)dipalladium(0) in toluene gave the mononuclear cyclometallated complexes [Pd{C6H4C(H)=NCH2CH2CH2NMe2}(Cl)] (2) and [Pd{3,4-(MeO)2C6H2C(H)=NCH2CH2CH2NMe2}(Br)] (21), respectively, via oxidative addition reaction with the ligand as a C,N,N terdentate ligand. Reaction of 2 with sodium bromide or iodide in an acetone–water mixture gave the cyclometallated analogues of 2, [Pd{C6H4C(H)=NCH2CH2CH2NMe2}(Br)] (3) and [Pd{C6H4C(H)=NCH2CH2CH2NMe2}(I)] (4), by halogen exchange. The X-ray crystal structures of 2, 3 and 4 were determined and discussed. Treatment of 2, 3, 4 and 21 with tertiary monophosphines in acetone gave the mononuclear cyclometallated complexes [Pd{C6H4C(H)=NCH2CH2CH2NMe2}(L)(X)] (6: L=PPh3, X=Cl; 7: L=PPh3, X=Br; 8: L=PPh3, X=I; 9: L=PMePh2, X=Cl; 10: L=PMe2Ph, X=Cl) and [Pd{3,4-(MeO)2C6H2C(H)=NCH2CH2CH2NMe2}(L)(Br)] (22: L=PPh3; 23: L=PMePh2; 24: L=PMe2Ph). A fluxional behaviour due to an uncoordinated CH2CH2CH2NMe2 could be determined by variable temperature NMR spectroscopy. Treatment of 2, 3 and 4 with silver trifluoromethanesulfonate followed by reaction with triphenylphosphine gave the mononuclear complex [Pd{C6H4C(H)=NCH2CH2CH2NMe2}(PPh3)][F3CSO3] (11) where the Pd–NMe2 bond was retained. Reaction of 2, 3 and 4 with ditertiary diphosphines in a cyclometallated complex–diphosphine 2:1 molar ratio gave the binuclear complexes [{Pd[C6H4C(H)=NCH2CH2CH2NMe2](X)}2(μ-L–L)][L–L=PPh2(CH2)4PPh2(dppb) (13, X=Cl; 14, X=Br; 15, X=I; L–L=PPh2(CH2)5PPh2(dpppe): 16, X=Cl; 17, X=Br; 18, X=I) with palladium–NMe2 bond cleavage. Treatment of 2, 3 and 4 with ditertiary diphosphines, in a cyclometallated complex–diphosphine 2:1, molar ratio and AgSO3CF3 gave the binuclear cyclometallated complexes [{Pd[C6H4C(H)=NCH2CH2CH2NMe2]}2(μ-L–L)][F3CSO3]2 (11: L–L=PPh2(CH2)4PPh2(dppb), X=Cl; 12: L–L=PPh2(CH2)5PPh2 (dpppe), X=Cl). Reaction of 2 with the ditertiary diphosphine cis-dppe in a cyclometallated complex–diphosphine 1:1 molar ratio followed by treatment with sodium perchlorate gave the mononuclear cyclometallated complex [Pd{C6H4C(H)=NCH2CH2CH2NMe2}(cis-PPh2CH=CHPPh2–P,P)][ClO4] (19). 相似文献
11.
Yann Sarazin 《Journal of organometallic chemistry》2006,691(26):5680-5687
The new heteroleptic mercury(II) complex PhHgN(SiMe3)2(1) reacts with the strong Brønsted acid [H(OEt2)2][H2N{B(C6F5)3}2] with cleavage of a N-Si bond to give [C6H5Hg(H2NSiMe3)][H2N{B(C6F5)3}2] (2), a phenyl-mercury(II) cation stabilised by a primary amine and a non-coordinating counter-anion. Attempts to generate donor-free aryl mercury cations were not successful. The crystal structure of 2 · CH2Cl2 shows short π-bonding interactions between the metal and the phenyl ring of a neighbouring cation; the geometry about the mercury(II) atom is nearly linear. The X-ray structures of the new salts [H2N(SiMe3)2 · H3NSiMe3][B(C6F5)4]2 and [Et3O][H2N{B(C6F5)3}2] · CH2Cl2 are also presented. 相似文献
12.
Stephan Back Martin Lutz Anthony L. Spek Heinrich Lang Gerard van Koten 《Journal of organometallic chemistry》2001,620(1-2)
A series of homodinuclear Pt compounds containing the anionic, potentially terdentate NCN ligand (NCN=[C6H3(Me2NCH2)2-2,6]−) or its 4-ethynyl derivative were prepared. The two platinum centres are linked together in two different fashions: (i) directly linked by an ethynyl or diethynylphenyl group (head-to-head) and (ii) indirectly bonded by a ethynyl- or butadiynyl-linked bis-NCN ligand (tail-to-tail). The reaction of the head-to-head σ,σ′-ethynylide complex {Pt}CC{Pt} ({Pt}=[Pt(C6H3{CH2NMe2}2-2,6)]+) with [CuCl]n yields {Pt}Cl and [Cu2C2]n, while with [Cu(NCMe)4][BF4] a Cu(I) bridged complex was formed: [(η2-{Pt}CC{Pt})2Cu][BF4]. The results of cyclic voltammetry experiments reveal that both connection modes of the two platinum centres lead to electrochemically independent Pt–NCN units. The X-ray crystal structure analysis of the neutral, tail-to-tail bridging butadiyne bis-NCNH ligand [C6H3(CH2NMe2)-1,3-(CC)-5]2 is reported. 相似文献
13.
Michael E. Peach 《Journal of fluorine chemistry》1982,20(5):669-675
The mass spectra of a number of thioethers of the type p-XC6H4SC6F5 (X = H, Cl, NO2, SC6F5, CO2C2H5, C6H5) have been examined. These spectra have been compared with those of (C6H5)2S and (C6F5)2S. Fragmentation patterns have been deduced from metastable peaks. The spectrum of p-ClC6H4SC6F5 has been studied in more detail. 相似文献
14.
A new method for the preparation of bis(perfluoroorgano) zinc compounds is described: CF3I and C6F5I react with dialkylzinc in the presence of a Lewis base quantitatively to give (CF3)2Zn and (C6F5)2Zn complexes, while the analogous reactions with C2F5I and iC3F7I do not yield the pure compounds. 1H, 19F n.m.r, i.r. and Raman spectra are presented. 相似文献
15.
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. 相似文献
16.
[Pd(C6F5)2(CNR)2] (R = Cy, But, p-MeC6H4 (p-Tol)) react with [PdCl2(NCPh)2] to give [Pd2(μ-Cl)2(C6F5)2(CNR)2]. In refluxing benzene insertion of isocyanide into the C6F5Pd bonds occurs only for R = p-Tol, to give a imidoyl bridged polynuclear complex cis-[Pd2 (μ-Cl)2[μ-C(C6F5) = N(Tol-p)]2n]. This complex reacts with (a) Tl(acac) to give [Pd2{μ-C(C6F5) = N(Tol-p)}2(acac)2]; (b) neutral monodentate ligands to afford dimeric complexes [Pd2{μ-C(C6F5) = N(Tol-p)}2Cl2L2] (L = NMe3, py, 4-Me-py, SC4H8), and (c) isocyanides to give insoluble complexes of the same composition which are thought to be polymeric, [(CNR)Cl{μ-C(C6F5) = (p-Tol)}]n (R = p-Tol, Me, But). Thermal decomposition of cis-[Pd2 (μ-Cl)2 [μ-C(C6F5) = N( p-Tol)]2n] gives the diazabutadiene species (p-Tol)NC(C6F5)C(C6F5)N(p-Tol) in high yield. 相似文献
17.
Vadim V. Bardin Dmitrii V. Trukhin Nicolay Yu. Adonin Vladimir F. Starichenko 《Journal of fluorine chemistry》2004,125(10):1431-1435
Dehalogenation of perhalogenated cyclohexanes C6Cl6F6, 1-azacyclohexenes C5Cl4F5N and bicyclo[4.4.0]dec-1(6)-enes C10Cl8F8 in the vapour phase over iron filings at 350-500 °C and in solution with Zn and additivities (Cu, NiCl2·6H2O + bpy) at 80 °C (heterogeneous reaction) or with P(NEt2)3 at 20 °C (homogeneous reaction) was studied. In all cases, perfluoroarenes, chloroperfluoroarenes and dichloroperfluoroarenes (benzenes, naphthalenes and pyridines) were obtained in good overall yield. 相似文献
18.
In attempts to form group 15 heteroalkynes, the reactions of Ar′C(O)Cl or Ar″C(O)Cl (Ar″ = C6H3(C6H2Me3-2,4,6)2-2,6) with [LiE(SiMe3)2] (E = P, As or Sb) have been carried out. No reactions occurred with the bulkier acid chloride, Ar′C(O)Cl, whilst reactions only occurred with Ar″C(O)Cl at elevated temperatures. One of these afforded the first terphenyl substituted phosphaalkyne, PCAr″, as an air stable, crystalline solid. The X-ray crystal structure of this compound was obtained. 相似文献
19.
The 31P chemical shift of the (C6H5)3-nPXn ligands (X = Cl, Br, I; n = 0–3) is dominated by the electronegativity of the substituents. π bonding is only important for derivatives with three strongly electronegative substituents. The 31P chemical shift of the corresponding complexes (C6H5)3-nPXnCr(CO)5 is governed by the simultaneous effects of the electronegativity, steric hindrance and π bonding. The resonance parameter, δ', indicates an increasing (pring → dp)π and (dcr→ dp)π electron delocalization with halogen substitution. 相似文献
20.
Maribel Arroyo Consuelo Mendoza Sylvain Berns Hugo Torrens Hugo Morales-Rojas 《Polyhedron》2009,28(13):2625-2634
The reactions of OsO4 with excess of HSC6F5 and P(C6H4X-4)3 in ethanol afford the five-coordinate compounds [Os(SC6F5)4(P(C6H4X-4)3)] where X = OCH3 1a and 1b, CH3 2a and 2b, F 3a and 3b, Cl 4a and 4b or CF3 5a and 5b. Single crystal X-ray diffraction studies of 1 to 5 exhibit a common pattern with an osmium center in a trigonal-bipyramidal coordination arrangement. The axial positions are occupied by mutually trans thiolate and phosphane ligands, while the remaining three equatorial positions are occupied by three thiolate ligands. The three pentafluorophenyl rings of the equatorial ligands are directed upwards, away from the axial phosphane ligand in the arrangement “3-up” (isomers a). On the other hand, 31P{1H} and 19F NMR studies at room temperature reveal the presence of two isomers in solution: The “3-up” isomer (a) with the three C6F5-rings of the equatorial ligands directed towards the axial thiolate ligand, and the “2-up, 1-down” isomer (b) with two C6F5-rings of the equatorial ligands directed towards the axial thiolate and the C6F5-ring of the third equatorial ligand directed towards the axial phosphane. Bidimensional 19F–19F NMR studies encompass the two sub-spectra for the isomers a (“3-up”) and b (“2-up, 1-down”). Variable temperature 19F NMR experiments showed that these isomers are fluxional. Thus, the 19F NMR sub-spectra for the “2-up, 1-down” isomers (b) at room temperature indicate that the two S-C6F5 ligands in the 2-up equatorial positions have restricted rotation about their C–S bonds, but this rotation becomes free as the temperature increases. Room temperature 19F NMR spectra of 3 and 5 also indicate restricted rotation around the Os–P bonds in the “2-up, 1-down” isomers (b). In addition, as the temperature increases, the 19F NMR spectra tend to be consistent with an increased rate of the isomeric exchange. Variable temperature 31P{1H} NMR studies also confirm that, as the temperature is increased, the a and b isomeric exchange becomes fast on the NMR time scale. 相似文献