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1.
The synthesis of a series of anionic half-sandwich ruthenium-arene complexes [E][RuCl26-p-cymene){PR2(p-Ph3BC6H4)}] (E = Bu4N+: R = Ph, 1a, iPr, 1b or Cy, 1c; E = bis(triphenylphosphine)iminium or PNP+: R = Ph, 1a′, iPr, 1b′ or Cy, 1c′) are reported. X-ray crystallographic studies of 1a′ and 1b′ confirmed the three-legged piano-stool coordination geometry. In solution, complexes 1a-c and 1a-c′ are proposed to form monomer-dimer equilibria as a result of chloride ligand dissociation. Complexes 1a-c and 1a-c′ also form the formally neutral zwitterionic complexes [RuCl(L)(η6-p-cymene){PR2(p-Ph3BC6H4)}] (L = pyridine: R = Ph, 2a, iPr, 2b or Cy, 2c; L = MeCN: R = Ph, 3a, iPr, 3b or Cy, 3c) via chloride ligand abstraction using AgNO3 or MeOTf.  相似文献   

2.
The synthesis, characterization and thermal behavior of new monomeric allylpalladium (II) complexes with dichalcogenoamidodiphosphinate anions are reported. The complexes [R = H, R′ = Pri, E = S (1a); R = H, R′ = Pri, E = Se (1b); R = H, R′ = Ph, E = S (1c); R = H, R′ = Ph, E = Se (1d); R = Me, R′ = Pri, E = S (2a); R = Me, R′ = Pri, E = Se (2b); R = Me, R′ = Ph, E = S (2c); R = Me, R′ = Ph, E = Se (2d)] have been prepared by room temperature reaction of [Pd(η3-CH2C(R)CH2)(acac)] (acac = acetylacetonate) with dichalcogenoimidodiphosphinic acids in acetonitrile solution. The complexes have been characterized by multinuclear NMR (1H, 13C{1H}, 31P{1H}, 77Se{1H}), FT-IR and elemental analyses. The crystal structures of complexes 1a, 1d and 2d have been reported and they consist of a six-membered PdE2P2N ring (E = S for 1a and Se for 1d and 2d) and an allyl group, C3H4R(R = H for 1a and 1d and Me for 2d). Thermogravimetric studies have been carried out for few representative complexes. The complexes thermally decompose in argon atmosphere to leave a residue of palladium chalcogenides, which have been characterized by PXRD, SEM and EDS.  相似文献   

3.
The reaction pathway for the formation of the trimethylsiloxysilyllithium compounds (Me3SiO)RR′SiLi (2a: R = Et, 2b: R = iPr, 2c: R = 2,4,6-Me3C6H2 (Mes); 2a-c: R′ = Ph; 2d: R = R′ = Mes) starting from the conversion of the corresponding trimethylsiloxychlorosilanes (Me3SiO)RR′SiCl (1a-d) in the presence of excess lithium in a mixture of THF/diethyl ether/n-pentane at −110 °C was investigated.The trimethylsiloxychlorosilanes (Me3SiO)RPhSiCl (1a: R = Et, 1b: R = iPr, 1c: R = Mes) react with lithium to give initially the trimethylsiloxysilyllithium compounds (Me3SiO)RPhSiLi (2a-c). These siloxysilyllithiums 2 couple partially with more trimethylsiloxychlorosilanes 1 to produce the siloxydisilanes (Me3SiO)RPhSi-SiPhR(OSiMe3) (Ia-c), and they undergo bimolecular self-condensation affording the trimethylsiloxydisilanyllithium compounds (Me3SiO)RPhSi-RPhSiLi (3a-c). The siloxydisilanes I are cleaved by excess of lithium to give the trimethylsiloxysilyllithiums (Me3SiO)RPhSiLi (2). In the case of the two trimethylsiloxydisilanyllithiums (Me3SiO)RPhSi-RPhSiLi (3a: R = Et, 3b: R = iPr) a reaction with more trimethylsiloxychlorosilanes (Me3SiO)RPhSiCl (1a, 1b) takes place under formation of siloxytrisilanes (Me3SiO)RPhSi-RPhSi-SiPhR(OSiMe3) (IIa: R = Et, IIb: R = iPr) which are cleaved by lithium to yield the trimethylsiloxysilyllithiums (Me3SiO)RPhSiLi (2a, 2b) and the trimethylsiloxydisilanyllithiums (Me3SiO)RPhSi-RPhSiLi (3a, 3b). The dimesityl-trimethylsiloxy-silyllithium (Me3SiO)Mes2SiLi (2d) was obtained directly by reaction of the trimethylsiloxychlorosilane (Me3SiO)Mes2SiCl (1d) and lithium without formation of the siloxydisilane intermediate. Both silyllithium compounds 2 and 3 were trapped with HMe2SiCl giving the products (Me3SiO)RR′Si-SiMe2H and (Me3SiO)RPhSi-RPhSi-SiMe2H.  相似文献   

4.
The reactions of the trimethylsiloxychlorosilanes (Me3SiO)RR′SiCl (1a-h: R′ = Ph, 1a: R = H, 1b: R = Me, 1c: R = Et, 1d: R = iPr, 1e: R = tBu, 1f: R = Ph, 1g: R = 2,4,6-Me3C6H2 (Mes), 1h: R = 2,4,6-(Me2CH)3C6H2 (Tip); 1i: R = R′ = Mes) with lithium metal in tetrahydrofuran (THF) at −78 °C and in a mixture of THF/diethyl ether/n-pentane in a volume ratio 4:1:1 at −110 °C lead to mixtures of numerous compounds. Dependent on the substituents silyllithium derivatives (Me3SiO)RR′SiLi (2b-i), Me3SiO(RR′Si)2Li (3a-g), Me3SiRR′SiLi (4a-h), (LiO)RR′SiLi (12e, 12g-i), trisiloxanes (Me3SiO)2SiRR′ (5a-i) and trimethylsiloxydisilanes (6f, 6h, 6i) are formed. All silyllithium compounds were trapped with Me3SiCl or HMe2SiCl resulting in the following products: (Me3SiO)RR′SiSiMe2R″ (6b-i: R″ = Me, 7c-i: R″ = H), Me3SiO(RR′Si)2SiMe2R″ (8a-g: R″ = Me, 9a-g: R″ = H), Me3SiRR′SiSiMe2R″ (10a-h: R″ = Me, 11a-h: R″ = H) and (HMe2SiO)RR′SiSiMe2H (13e, 13g-i). The stability of trimethylsiloxysilyllithiums 2 depends on the substituents and on the temperature. (Me3SiO)Mes2SiLi (2i) is the most stable compound due to the high steric shielding of the silicon centre. The trimethylsiloxysilyllithiums 2a-g undergo partially self-condensation to afford the corresponding trimethylsiloxydisilanyllithiums Me3SiO(RR′Si)2Li (3a-g). (Me3)Si-O bond cleavage was observed for 2e and 2g-i. The relatively stable trimethylsiloxysilyllithiums 2f, 2g and 2i react with n-butyllithium under nucleophilic butylation to give the n-butyl-substituted silyllithiums nBuRR′SiLi (15g, 15f, 15i), which were trapped with Me3SiCl. By reaction of 2g and 2i with 2,3-dimethylbuta-1,3-diene the corresponding 1,1-diarylsilacyclopentenes 17g and 17i are obtained.X-ray studies of 17g revealed a folded silacyclopentene ring with the silicon atom located 0.5 Å above the mean plane formed by the four carbon ring atoms.  相似文献   

5.
The diiron complexes [Fe(Cp)(CO){μ-η22-C[N(Me)(R)]NC(C6H3R′)CCH(Tol)}Fe(Cp)(CO)] (R = Xyl, R′ = H, 3a; R = Xyl, R′ = Br, 3b; R = Xyl, R′ = OMe, 3c; R = Xyl, R′ = CO2Me, 3d; R = Xyl, R′ = CF3, 3e; R = Me, R′ = H, 3f; R = Me, R′ = CF3, 3g) are obtained in good yields from the reaction of [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(p-NCC6H4R′)(Cp)2]+ (R = Xyl, R′ = H, 2a; R = Xyl, R′ = Br, 2b; R = Xyl, R′ = OMe, 2c; R = Xyl, R′ = CO2Me, 2d; R = Xyl, R′ = CF3, 2e; R = Me, R′ = H, 2f; R = Me, R′ = CF3, 2g) with TolCCLi. The formation of 3 involves addition of the acetylide at the coordinated nitrile and C-N coupling with the bridging aminocarbyne together with orthometallation of the p-substituted aromatic ring and breaking of the Fe-Fe bond. Complexes 3a-e which contain the N(Me)(Xyl) group exist in solution as mixtures of the E-trans and Z-trans isomers, whereas the compounds 3f,g, which posses an exocyclic NMe2 group, exist only in the Z-cis form. The crystal structures of Z-trans-3b, E-trans-3c, Z-trans-3e and Z-cis-3g have been determined by X-ray diffraction experiments.  相似文献   

6.
The ortho-metallated complexes [Pd22(C,C)-C6H4(PPh2CHC(O)C6H5R}2(μ-Cl)2] (R = Ph (1a), NO2 (1b), Br (1c)) were prepared by refluxing equimolar mixtures of Ph3PCHC(O)C6H5R, (R = Ph, NO2, Br) and Pd(OAc)2 in MeOH, followed by an excess of NaCl. The dinuclear complexes (1a-1c) react with silver trifluoromethylsulfonate and bidentate ligands [L = bipy (2,2′-bipyridine), phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), dppp (bis(diphenylphosphino)propane)] giving the mononuclear stabilized orthopalladated complexes in endo position [Pd{κ2(C,C)-C6H4(PPh2CHC(O)R}L](OTf) [R = Ph, L = phen (2a), bipy (3a), dppe (4a), dppp (5a); R = NO2, L = phen (2b), bipy (3b), dppe (4b), dppp (5b); R = Br, L = phen (2c), bipy (3c), dppe (4c), dppp (5c); OTf = trifluoromethylsulfonate anion]. Orthometalation and ylidic C-coordination are demonstrated by an X-ray diffraction study of 2c and 3c. In the structures, the palladium atom shows a slightly distorted square-planar coordination geometry.  相似文献   

7.
N-thioamide thiosemicarbazone derived from 4-(methylthio)benzaldehyde (R = H, HL1; R = Me, HL2 and R = Ph, HL3) have been prepared and their reaction with fac-[ReX(CO)3(CH3CN)2] (X = Br, Cl) in methanol gave the adducts [ReX(CO)3(HLn)] (1a X = Cl, n = 1; 1a′ X = Br, n = 1; 1b X = Cl, n = 2; 1b′ X = Br, n = 2; 1c X = Cl, n = 3; 1c′ X = Br, n = 3) in good yield.All the compounds have been characterized by elemental analysis, mass spectrometry (ESI), IR and 1H NMR spectroscopic methods. Moreover, the structures of HL2, HL3, HL3·(CH3)2SO and 1b′·H2O were also elucidated by X-ray diffraction. In 1b′, the rhenium atom is coordinated by the sulphur and the azomethine nitrogen atoms (κS,N3) forming a five-membered chelate ring, as well as three carbonyl and bromide ligands. The resulting coordination polyhedron can be described as a distorted octahedron.The structure of the dimers is based on rhenium(I) thiosemicarbazonates [Re2(L1)2(CO)6] (2a), [Re2(L2)2(CO)6] (2b) and [Re2(L3)2(CO)6] (2c) as determined by X-ray studies. Methods of synthesis were optimized to obtain amounts of these thiosemicarbazonate complexes. In these compounds the dimer structures are achieved by Re-S-Re bridges, where S is the thiolate sulphur from a κS,N3-bidentate thiosemicarbazonate ligand.Some single crystals isolated in the synthesis of 2b contain [Re(L4)(L2)(CO)3] (3b) where L4 (=2-methylamine-5-(para-methylsulfanephenyl)-1,3,4-thiadiazole) is originated in a cyclization process of the thiosemicarbazone. Furthermore, the rhenium atom is coordinate by the sulphur and the thioamidic nitrogen of the thiosemicarbazonate (κS,N2) affording a four-membered chelate ring.  相似文献   

8.
The dialkyl complexes, (R = Pri, R′ = Me (2a), CH2Ph (3a); R = Bun, R′ = Me (2b), CH2Ph (3b); R = But, R′ = Me (2c), CH2Ph (3c); R = Ph, R′ = Me (2d), CH2Ph (3d)), have been synthesized by the reaction of the ansa-metallocene dichloride complex, [Zr{R(H)C(η5-C5Me4)(η5-C5H4)}Cl2] (R = Pri (1a), Bun (1b), But (1c), Ph (1d)), and two molar equivalents of the alkyl Gringard reagent. The insertion reaction of the isocyanide reagent, CNC6H3Me2-2,6, into the zirconium-carbon σ-bond of 2 gave the corresponding η2-iminoacyl derivatives, [Zr{R(H)C(η5-C5Me4)(η5-C5H4)}{η2-MeCNC6H3Me2-2,6}Me] (R = Pri (4a), Bun (4b), But (4c), Ph (4d)). The molecular structures of 1b, 1c and 3b have been determined by single-crystal X-ray diffraction studies.  相似文献   

9.
Primary alkynes R′CCH [R′ = Me3Si, Tol, CH2OH, CO2Me, (CH2)4CCH, Me] insert into the metal-carbon bond of diruthenium μ-aminocarbynes [Ru2{μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp)2][SO3CF3] [R = 2,6-Me2C6H3 (Xyl), 1a; CH2Ph (Bz), 1b; Me, 1c] to give the vinyliminium complexes [Ru2{μ-η13-C(R′)CHCN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] [R = Xyl, R′ = Me3Si, 2a; R = Bz, R′ = Me3Si, 2b; R = Me, R′ = Me3Si, 2c; R = Xyl, R′ = Tol, 3a; R = Bz, R′ = Tol, 3b; R = Bz, R′ = CH2OH, 4; R = Bz, R′ = CO2Me, 5a; R = Me, R′ = CO2Me, 5b; R = Xyl, R′ = (CH2)4CCH, 6; R = Xyl, R′ = Me, 7a; R = Bz, R′ = Me, 7b; R = Me, R′ = Me, 7c]. The related compound [Ru2{μ-η13-C[C(Me)CH2]CHCN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3], (9) is better prepared by reacting [Ru2{μ-CN(Me)(Xyl)}(μ-CO)(CO)(Cl)(Cp)2] (8) with AgSO3CF3 in the presence of HCCC(Me)CH2 in CH2Cl2 at low temperature.In a similar way, also secondary alkynes can be inserted to give the new complexes [Ru2{μ-η13-C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = Bz, R′ = CO2Me, 11; R = Xyl, R′ = Et, 12a; R = Bz, R′ = Et, 12b; R = Xyl, R′ = Me, 13). The reactions of 2-7, 9, 11-13 with hydrides (i.e., NaBH4, NaH) have been also studied, affording μ-vinylalkylidene complexes [Ru2{μ-η13-C(R′)C(R″)C(H)N(Me)(R)}(μ-CO)(CO)(Cp)2] (R = Bz, R′ = Me3Si, R″ = H, 14a; R = Me, R′ = Me3Si, R″ = H, 14b; R = Bz, R′ = Tol, R″ = H, 15; R = Bz, R′ = R″ = Et, 16), bis-alkylidene complexes [Ru2{μ-η12-C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (R′ = Me3Si, R″ = H, 17; R′ = R″ = Et, 18), acetylide compounds [Ru2{μ-CN(Me)(R)}(μ-CO)(CO)(CCR′)(Cp)2] (R = Xyl, R′ = Tol, 19; R = Bz, R′ = Me3Si, 20; R = Xyl, R′ = Me, 21) or the tetranuclear species [Ru2{μ-η12-C(Me)CCN(Me)(Bz)}(μ-CO)(CO)(Cp)2]2 (23) depending on the properties of the hydride and the substituents on the complex. Chromatography of 21 on alumina results in its conversion into [Ru2{μ-η31-C[N(Me)(Xyl)]C(H)CCH2}(μ-CO)(CO)(Cp)2] (22). The crystal structures of 2a[CF3SO3] · 0.5CH2Cl2, 12a[CF3SO3] and 22 have been determined by X-ray diffraction studies.  相似文献   

10.
A series of organotin(IV) complexes with O,O-diethyl phosphoric acid (L1H) and O,O-diisopropyl phosphoric acid (L2H) of the types: [R3Sn · L]n (L = L1, R = Ph 1, R = PhCH22, R = Me 3, R = Bu 4; L = L2, R = Ph 9, R = PhCH210, R = Me 11, R = Bu 12), [R2Cl Sn · L]n (L = L1, R = Me 5, R = Ph 6, R = PhCH27, R = Bu 8; L = L2, R = Me 13, R = Ph 14, R = PhCH215, R = Bu 16), have been synthesized. All complexes were characterized by elemental analysis, TGA, IR and NMR (1H, 13C, 31P and 119Sn) spectroscopy analysis. Among them, complexes 1, 2, 3, 5, 8, 9 and 11 have been characterized by X-ray crystallography diffraction analysis. In the crystalline state, the complexes adopt infinite 1D infinite chain structures which are generated by the bidentate bridging phosphonate ligands and the five-coordinated tin centers.  相似文献   

11.
Five non-symmetrical PCN pincer palladium(II) complexes [PdCl{C6H3-2-(CHNR)-6-()}] (R = m-ClC6H4, R′ = Ph (2a); R = Ph, R′ = Ph (2b); R = i-Pr, R′ = Ph (2c); R = m-ClC6H4, R′ = i-Pr (2d); R = (S)-1-phenylethyl, R′ = Ph (2e)) have been easily prepared in only two steps from readily available m-hydroxybenzaldehyde and characterized by HRMS, 1H NMR, 13C NMR, 31P NMR and IR spectra. The molecular structures of 2a and 2b have been further determined by X-ray single-crystal diffraction. The obtained Pd complexes were found to be effective catalysts for the Suzuki and copper-free Sonogashira cross-coupling reactions which could be carried out in the undried solvent under air.  相似文献   

12.
New μ-vinylalkylidene complexes cis-[Fe2{μ-η13-Cγ(R′)Cβ(R″)CαHN(Me)(R)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = R″ = Me, 3a; R = Me, R′ = R″ = Et, 3b; R = Me, R′ = R″ = Ph, 3c; R = CH2Ph, R′ = R″ = Me, 3d; R = CH2Ph, R′ = R″ = COOMe, 3e; R = CH2 Ph, R′ = SiMe3, R″ = Me, 3f) have been obtained b yreacting the corresponding vinyliminium complexes [Fe2{μ-η13-Cγ(R′)Cβ(R″)CαN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (2a-f) with NaBH4. The formation of 3a-f occurs via selective hydride addition at the iminium carbon (Cα) of the precursors 2a-f. By contrast, the vinyliminium cis-[Fe2{μ-η13-Cγ (R′) = Cβ(R″)Cα = N(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (R′ = R″ = COOMe, 4a; R′ = R″ = Me, 4b; R′ = Prn, R″ = Me, 4c; Prn = CH2CH2CH3, Xyl = 2,6-Me2C6H3) undergo H addition at the adjacent Cβ, affording the bis-alkylidene complexes cis-[Fe2{μ-η12-C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (5a-c). The cis and trans isomers of [Fe2{μ-η13-Cγ(Et)Cβ(Et)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4d) react differently with NaBH4: the former reacts at Cα yielding cis-[Fe2{μ-η13-Cγ(Et)Cβ(Et)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], 6a, whereas the hydride attack occurs at Cβ of the latter, leading to the formation of the bis alkylidene trans-[Fe2{μ-η12-C(Et)C(H)(Et)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (5d). The structure of 5d has been determined by an X-ray diffraction study. Other μ-vinylalkylidene complexes cis-[Fe2{μ-η13-Cγ(R′)Cβ(R″)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (R′ = R″ = Ph, 6b; R′ = R″ = Me, 6c) have been prepared, and the structure of 6c has been determined by X-ray diffraction. Compound 6b results from treatment of cis-[Fe2{μ-η13-Cγ(Ph)Cβ(Ph)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4e) with NaBH4, whereas 6c has been obtained by reacting 4b with LiHBEt3. Both cis-4d and trans-4d react with LiHBEt3 affording cis-6a.  相似文献   

13.
The synthesis of new organotin compounds of general formula Tip2SnRR′ (Tip = 2,4,6-triisopropylbenzene; R = R′ = CH3 (1); R = R′ = CHCH2 (2); R = CH2Ph, R′ = Br (3); R = R′ = CH2CHCH2 (4)) is described herein. The compounds have been characterized by 1H, 13C, 119Sn NMR, mass spectroscopy and elemental analysis. Characterization by single-crystal X-ray diffraction analysis has been obtained for compounds 2, 3 and 4. The reactivity with ionizing agents has been studied by NMR spectroscopy. Compounds 2 and 4 underwent alkyl abstraction by [(CH3CH2)3Si]+[B(C6F5)4] affording stable cationic species (2a, 4a). For the cationic specie 4a a π-interaction of the benzyl group to the metal centre was recognized by solution NMR studies. A cationic species (3a) was generated from compound 3 using AgSbF6 as ionizing agent. The cationic species (2a, 3a) exhibited moderate activity as initiator in the cationic polymerization of 1,4-butadiene and good activity in the ring opening polymerization (ROP) of propylene oxide and ε-caprolactone.  相似文献   

14.
The zwitterionic vinyliminium complex [Fe2{μ-η13-C(R′)C(S)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (2a) (R′ = p-Me-C6H4 (Tol), Xyl = 2,6-Me2C6H3) undergoes electrophilic addition at the S atom by HSO3CF3, MeSO3CF3, SiMe3Cl, BrCH2Ph, ICH2CHCH2 affording the complexes [Fe2{μ-η13-C(Tol)C(SX)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][Y] (X =  H, Y = SO3CF3, 4a; X = Me, Y = SO3CF3, 4b; X = SiMe3, Y = Cl, 4c; X = CH2Ph, Y = Br, 4d; X = CH2CHCH2, Y = I, 4e).Compound 2a and the corresponding vinyliminium complexes 2b and 2c (R′ = CH2OH, 2b; R′ = Me, 2c) react also with etherated BF3 leading to the formation of the corresponding S-adducts [Fe2{μ-η13-C(R′)C(SBF3)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (R′ = Tol, 5a; R′ = CH2OH, 5b; R′ = Me, 5c).In analogous reactions, the zwitterionic vinyliminium complexes undergo S-metalation upon treatment with in situ generated [Fp]+[SO3CF3] [Fp = Fe(CO)2(Cp)], leading to the formation of [Fe2{μ-η13-C(R′)C(S-Fp)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3](R′ = CH2OH, 6a; R′ = Me, 6b; R′ = Bun, 6c).Similarly, zwitterionic vinyliminium containing Se in the place of S also undergo Se-electrophilic addition. Thus, the complexes [Fe2{μ-η13-C(R′)C(SeX)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = X = Me, R′ = Tol, 7a; R = Xyl, R′ = Me, X = Fp+, 7b) are obtained upon treatment of the neutral zwitterionic precursors with MeSO3CF3 and [Fp][SO3CF3], respectively.Alkylation at the S or Se atom of the bridging ligand is also accomplished by CH2Cl2, used as solvent, although the reaction is slower compared to more efficient alkylating reagents. The complexes formed by this route are [Fe2{μ-η13-C(R′)C(E-CH2Cl)CN(Me)(R)}(μ-CO)(CO)(Cp)2][X] [E = S, R = Xyl, R′ = Tol, X = Cl, 8a; E = S, R = Xyl, R′ = Me, X = Cl, 8b; E = Se, R = R′ = Me, X = BPh4, 8c].Finally, treatment of the zwitterionic vinyliminium complexes with I2 results in the oxidative coupling with formation of S-S (disulfide) or Se-Se (diselenide) bond. The reactions, performed in the presence of NaBPh4 afford the tetranuclear complexes [Fe2{μ-η13-C(R′)C(E)CN(Me)(R)}(μ-CO)(CO)(Cp)2]2[BPh4]2 [R = Xyl, R′ = CH2OH, E = S, 9a; R = Xyl, R′ = Me, E = S, 9b; R = Xyl, R′ = Bun, E = S, 9c; R = Xyl, R′ = Me, E = Se, 9d; R = Me, R′ = Bun, E = Se, 9e].The molecular structures of 4a, 8c and 9e have been determined by X-ray diffraction studies.  相似文献   

15.
The bridging diiron thiocarbyne complex [Fe2{μ-CS(Me)}(μ-CO)(CO)2(Cp)2][SO3CF3] (1) reacts with activated olefins (methyl acrylate, acrylonitrile, styrene, diethyl maleate), in the presence of Me3NO and NaH, to give the corresponding μ-allylidene complexes [Fe2{μ-η13-Cα(SMe)Cβ(R′)Cγ(H)(R″)} (μ-CO)(CO)(Cp)2] (R″ = CO2Me, R′ = H, 3a; R″ = CN, R′ = H, 3b; R″ = C6H5, R′ = H, 3c; R″ = R′ = CO2Et, 3d). The coupling reaction of olefin with thiocarbyne is regio- and stereospecific, leading to the formation of only one isomer. C-C bond formation occurs between the less substituted alkene carbon and the thiocarbyne. Moreover, olefinic hydrogens of the bridging ligands are mutually trans.The reactions of 3a-b with MeSO3CF3 result, selectively, in the formation of the cationic μ-sulphonium allylidene complexes [Fe2{μ-η13-Cα(SMe2)Cβ (H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CO2Me, 4a; R = CN, 4b). Compound 4a undergoes displacement of the SMe2 group by nucleophiles such as NaBH4, NBu4CN and NaOMe, affording the complexes [Fe2{μ-η13-Cα(R)Cβ (H)Cγ(H)(CO2Me)}(μ-CO)(CO)(Cp)2] (R = H, 5a; R = CN, 5b; R = OMe, 5c), respectively. The molecular structures of 3a and 5a have been determined by X-ray diffraction studies.  相似文献   

16.
Eight new organoantimony(V) complexes with 1-phenyl-1H-tetrazole-5-thiol [L1H] and 2,5-dimercapto-4-phenyl-1,3,4-thiodiazole [L2H] of the type RnSbL5 − n (L = L1: n = 4, R = n-Bu 1, Ph 2, n = 3, R = Me 3, Ph 4; L = L2: n = 4, R = n-Bu 5, Ph 6, n = 3, R = Me 7, Ph 8) have been synthesized. All the complexes 1-8 have been characterized by elemental, FT-IR, 1H and 13C NMR analyses. Among them complexes 2, 6 and 8 have also been confirmed by X-ray crystallography. The structure analyses show that the antimony atoms in complexes 2 and 6 display a trigonal bipyramid geometry, while it displays a distorted capped trigonal prism in complex 8 with two intramolecular Sb?N weak interactions. Furthermore, the supramolecular structure of 2 has been found to consist of one-dimensional linear molecular chain built up by intermolecular C-H?N weak hydrogen bonds, while a macrocyclic dimer has been found in complex 6 linked by intermolecular C-H?S weak hydrogen bonds with head-to-tail arrangement. Interestingly, one-dimensional helical chain is recognized in complex 8, which is connected by intermolecular C-H?S weak hydrogen bonds.  相似文献   

17.
The bridging aminocarbyne complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3] (R = Me, 1a; Xyl, 1b; 4-C6H4OMe, 1c; Xyl = 2,6-Me2C6 H3) react with acrylonitrile or methyl acrylate, in the presence of Me3NO and NaH, to give the corresponding μ-allylidene complexes [Fe2{μ-η13- Cα(N(Me)(R))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = CN, 3a; R = Xyl, R′ = CN, 3b; R = 4-C6H4OMe, R′ = CN, 3c; R = Me, R′ = CO2Me, 3d; R = 4-C6H4OMe, R′ = CO2Me, 3e). Likewise, 1a reacts with styrene or diethyl maleate, under the same reaction conditions, affording the complexes [Fe2{μ-η13-Cα(NMe2)Cβ(R′)Cγ(H)(R″)}(μ-CO)(CO)(Cp)2] (R′ = H, R″ = C6H5, 3f; R′ = R″ = CO2Et, 3g). The corresponding reactions of [Ru2{μ-CN(Me)(CH2Ph)}(μ-CO)(CO)2(Cp)2][SO3CF3] (1d) with acrylonitrile or methyl acrylate afford the complexes [Ru2{μ-η13-Cα(N(Me)(CH2Ph))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R′ = CN, 3h; CO2Me, 3i), respectively.The coupling reaction of olefin with the carbyne carbon is regio- and stereospecific, leading to the formation of only one isomer. C-C bond formation occurs selectively between the less substituted alkene carbon and the aminocarbyne, and the Cβ-H, Cγ-H hydrogen atoms are mutually trans.The reactions with acrylonitrile, leading to 3a-c and 3h involve, as intermediate species, the nitrile complexes [M2{μ-CN(Me)(R)}(μ-CO)(CO)(NC-CHCH2)(Cp)2][SO3CF3] (M = Fe, R = Me, 4a; M = Fe, R = Xyl, 4b; M = Fe, R = 4-C6H4OMe, 4c; M = Ru, R = CH2C6H5, 4d).Compounds 3a, 3d and 3f undergo methylation (by CH3SO3CF3) and protonation (by HSO3CF3) at the nitrogen atom, leading to the formation of the cationic complexes [Fe2{μ-η13-Cα(N(Me)3)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 5a; R = CO2Me, 5b; R = C6H5, 5c) and [Fe2{μ-η13-Cα(N(H)(Me)2)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 6a; R = CO2Me, 6b; R = C6H5, 6c), respectively.Complex 3a, adds the fragment [Fe(CO)2(THF)(Cp)]+, through the nitrile functionality of the bridging ligand, leading to the formation of the complex [Fe2{μ-η13-Cα(NMe2)Cβ(H)Cγ(H)(CNFe(CO)2Cp)}(μ-CO)(CO)(Cp)2][SO3CF3] (9).In an analogous reaction, 3a and [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3], in the presence of Me3NO, are assembled to give the tetrameric species [Fe2{μ-η13-Cα(NMe2)Cβ(H)Cγ(H)(CN[Fe2{μ- CN(Me)(R)}(μ-CO)(CO)(Cp)2])}(μ-CO)(CO)(Cp)2][SO3CF3] (R = Me, 10a; R = Xyl, 10b; R = 4-C6H4OMe, 10c).The molecular structures of 3a and 3b have been determined by X-ray diffraction studies.  相似文献   

18.
Four cyclometalated Pt(II) complexes, i.e., [(L2)PtCl] (1b), [(L3)PtCl] (1c), [(L2)PtCCC6H5] (2b) and [(L3)PtCCC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2′-bipyridine and HL3 = 4-[p-(N,N′-dibutyl-N′-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2′-bipyridine), have been synthesized and verified by 1H NMR, 13C NMR and X-ray crystallography. Unlike previously reported complexes [(L1)PtCl] (1a) and [(L1)PtCCC6H5] (2a) (HL1 = 4,6-diphenyl-2,2′-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer (1MLCT) (dπ(Pt) → π(L)) transitions (ε ∼ 2 × 104 dm3 mol−1 cm−1) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c. Meanwhile, with the introduction of electron-donating arylamino groups in the ligands of 1a and 2a, complexes 1b and 2b display stronger phosphorescence in CH2Cl2 solutions at room temperature with bathochromically shifted emission maxima at 595 and 600 nm, relatively higher quantum yields of 0.11 and 0.26, and much longer lifetimes of 8.4 and 4.5 μs, respectively. An electrochromic film of 1b-based polymer was obtained on Pt or ITO electrode surface, which suggests an efficient oxidative polymerization behavior. An orange multilayer organic light-emitting diode with 1b as phosphorescent dopant was fabricated, achieving a maximum current efficiency of 11.3 cd A−1 and a maximum external efficiency of 5.7%. The luminescent properties of complexes 1c and 2c are dependent on pH value and solvent polarity, which is attributed to the protonation of arylamino units in the C^N^N cyclometalating ligands.  相似文献   

19.
New boron substituted cobalta bis(dicarbollide)(1-) ion (1) derivatives of formula [(8,8′-(RPhP(O)(CH2)nC(O)N) < (1,2-C2B9H10)2-3,3′-Co] (R = Ph or C8H17, n = 1, 3a, 3b; R = Ph, n = 2, 3c), [(8-(Ph2P(O)CH2C(O)NR)(1,2-C2B9H10))(1′,2′-C2B9H11)-3,3′-Co] (R = H, C2H5, CH2C6H5, 5a-c) and [(8-(2RPhP(O)CH2C(O)N(1R)CH2-1,2-C2B9H10))(8′-CH3O-1′,2′-C2B9H10)-3,3′-Co] (1R = Benzyl, 2R = Ph or C8H17, 7a,b) were prepared with the aim to develop a new class of efficient extraction agents for partitioning of polyvalent f-block elements, i.e. lanthanides and actinides from high-level activity nuclear waste. The anionic ligands were characterized by multinuclear NMR spectroscopy and MS, the structures of Cs3a and the calcium complex of 7a were determined by X-ray diffraction analysis. The crystallographic study of the Cs3a proved a formation of linear chains in the structure, where the metal cation is coordinated by oxygen atoms of the CMPO terminal groups. The X-ray structure of the Ca2+ complex of the ionic ligand 7a proved a 1:3 metal to ligand ratio. Presented also is the X-ray structure of the starting ammonium compound 6 used in the synthesis of 7a and 7b. With exception of 5c, these anionic ligands are of high extraction efficiency, the highest being found for 7a in low polar solvent mixture hexyl methyl ketone-dodecane 1:1. These properties qualify some of these derivatives for possible technological applications.  相似文献   

20.
A series of titanocene(III) alkoxides L2Ti(III)OR where L = Cp, R = Et(1b), tBu(1a), 2,6-Me2C6H3(1c), 2,6-tBu2-4-Me-C6H2(1d), or L = Cp*, R = Me(2e), tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO)3]2 [M = Mo, W], [CpRu(CO)2]2, and Co2(CO)8. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO)3]2 [M = Mo, W] to form heterobimetallic complexes L2Ti(OR)(μ-OC)(CO)2MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co2(CO)8 resulted in formation of Ti-Co1 heterobimetallic complexes, from 2a, 2e, or 2f, or Ti-Co3 tetrametallic complexes, Cp2Ti(OtBu)(μ-OC)Co3(CO)9 from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.  相似文献   

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