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1.
Treatment of the hydrosulfido tungsten complex CpW(CO)3SH with acid chlorides (RCOCl) or sulfonyl chlorides (RSO2Cl) affords CpW(CO)3SCOR (1) [R = Me (a), CH2Cl (b), Ph (c), 4-C6H4NO2 (d)] and CpW(CO)3SSO2R (2) [R = Me (a), Ph (b), 4-C6H4Cl (c), 4-C6H4NO2 (d)], respectively. The novel complexes, 1 and 2, were fully characterized by elemental analyses, IR and 1H NMR spectroscopy. The solid state structures of CpW(CO)3SCOPh (1c) and CpW(CO)3SSO2-4-C6H4Cl (2c) were determined by an X-ray crystal structure analysis.  相似文献   

2.
Reaction of 2-benzoylpyridine thiosemicarbazone (H2Bz4DH, HL1) and its N(4)-methyl (H2Bz4Me, HL2) and N(4)-phenyl (H2Bz4Ph, HL3) derivatives with SnCl4 and diphenyltin dichloride (Ph2SnCl2) gave [Sn(L1)Cl3] (1), [Sn(L1)PhCl2] (2), [Sn(L2)Cl3] (3), (4) [Sn(L3)PhCl2] (5) and [Sn(L3)Ph2Cl] (6). Infrared and 1H, 13C and 119Sn NMR spectra of 1-3, 5 and 6 are compatible with the presence of an anionic ligand attached to the metal through the Npy-N-S chelating system and formation of hexacoordinated tin complexes. The crystal structures of 1-3, 5 and 6 show that the geometry around the metal is a distorted octahedron formed by the thiosemicarbazone and either chlorides or chlorides and phenyl groups. The crystal structure of 4 reveals the presence of and trans [Ph2SnCl4]2−.  相似文献   

3.
(Z)-5-(2-(1H-Indol-3-yl)-2-oxoethylidene)-3-phenyl-2-thioxothiazolidin-4-one (7a-q) derivatives have been synthesized by the condensation reaction of 3-phenyl-2-thioxothiazolidin-4-ones (3a-h) with suitably substituted 2-(1H-indol-3-yl)-2-oxoacetaldehyde (6a-d) under microwave condition. The thioxothiazolidine-4-ones were prepared from the corresponding aromatic amines (1a-e) and di-(carboxymethyl)-trithiocarbonyl (2). The aldehydes (6a-h) were synthesized from the corresponding acid chlorides (5a-d) using HSnBu3.  相似文献   

4.
New pyridine-phosphine chalcogenide ligands, tris[2-(2-pyridyl)ethyl]phosphine sulfide 1a and tris[2-(2-pyridyl)ethyl]phosphine selenide 1b, react with zinc(II) and cadmium(II) chlorides in EtOH at room temperature to afford complexes of compositions 2ZnCl2·2L (2, L = 1a) and 3CdCl2·2L (3a,b, L = 1a,b) in high yields. The solid-state structure of complexes 2, 3 has been proved by X-ray analysis data. Complex 2 is a centrosymmetric dimer, where two atoms of zinc are bonded by two bridging pyridine-phosphine sulfide ligands through N atoms. Complexes 3a,b exist as polymeric chains with each bridging ligand acting as a chelate N,S- or N,Se-donor to one cadmium(II) center and as a pyridine N-donor to the next cadmium(II) center.  相似文献   

5.
(5Z,5′Z)-3,3′-(1,4-Phenylenebis(methylene)-bis-(5-arylidene-2-thioxothiazolidin-4-one) derivatives (5a-r) have been synthesized by the condensation reaction of 3,3′-(1,4- or 1,3-phenylenebis(methylene))bis(2-thioxothiazolidin-4-ones) (3a,b) with suitably substituted aldehydes (4a-f) or 2-(1H-indol-3-yl)2-oxoacetaldehydes (8a-c) under microwave conditions. The bis(2-thioxothiazolidin-4-ones) were prepared from the corresponding primary alkyl amines (1a,b) and di-(carboxymethyl)-trithiocarbonyl (2). The 2-(1H-indol-3-yl)-2-oxoacetaldehydes (8a-c) were synthesized from the corresponding acid chlorides (7a-c) using HSnBu3.  相似文献   

6.
(R)-4-Ethyl-2-(1,1-dimethylpropyl)-2-oxazoline (1) and (S)-4-tert-butyl-2-(1,1-dimethylbutyl)-2-oxazoline (2) were synthesized in two steps from the corresponding enantiopure amino alcohols and acid chlorides in a total yield of 95% and 72%, respectively. (S)-2-(1-Adamantyl-1-methylethyl)-4-isobutyl-2-oxazoline (3) was obtained from adamantyl bromide and l-leucinol in five steps in a total yield of 82%. Reactions of oxazolines 13 with Pd(OAc)2 in AcOH or CH2Cl2 followed by treatment with LiCl afforded the corresponding μ-Cl dimeric cyclopalladated complexes 15, 17, and 20 in good yield. Compounds 15, 17, and 20 reacted with PPh3 to furnish the corresponding mononuclear complexes 16, 19, and 21. The 31P NMR spectra of trans(N,P) adducts 16, 19, and 21 contained signals of two diastereomers in a ratio of ca. 1.3:1.  相似文献   

7.
A series of palladium complexes (C1-C7) have been prepared by the reaction of PdCl2(CH3CN)2 with 2-methoxycarbonyl-6-iminopyridines, L1-L7. The 2-methoxycarbonyl-6-iminopyridines and their complexes were fully characterized by FT-IR, NMR spectra and elemental analysis. Structures of C1, C2, C4, C5 and C6, C7 were determined by X-ray crystallography, and these complexes fold slightly distorted square planar structures around palladium coordinated with two nitrogen atoms and two chlorides. These palladium complexes exhibited moderate catalytic activities for ethylene dimerization and/or polymerization in the presence of methylaluminoxane, and showed remarkable catalytic activity for norbornene polymerization. The catalytic behaviors of these complexes were highly affected by both the ligand employed and reaction conditions.  相似文献   

8.
The cyclopropyl chlorides (1 and 2) rearrange on heating to give stereospecifically the allyl chlorides (3 and 4, respectively). In the presence of nucleophiles such as methoxide ion, the corresponding allyl ethers (5 and 6, respectively) are formed. Analysis of the stereochemistry of these products indicates that they are formed from the corresponding allyl chlorides (3 and 4), which are evidently the first-formed products of the reaction even in the presence of strong nucleophiles. The reaction of the allyl chlorides (3 and 4) with sodium phenylthioxide in aprotic non-polar solvents goes predominantly with retention of configuration, but in methanol is normal in giving predominantly inversion of configuration.  相似文献   

9.
[Ni2(iPr2Im)4(COD)] 1 catalyzes the Suzuki-Miyaura-type cross coupling reaction of chlorobenzene and phenylboronic acid efficiently. Compound 1 compares well with other nickel catalyst reported so far with the advantage that no further excess of ligand such as PPh3 has to be added. Oxidative addition of different aryl chlorides to complex 1 is highly selective for a broad range of substrates, ranging from activated to deactivated aryl chlorides. The stoichiometric reaction of 1 with aryl chlorides (ArCl) afforded complexes of the type trans-[Ni(iPr2Im)2(Cl)(Ar)] (for Ar = Ph 2, 4-Me(O)CC6H43, 4-H(O)CC6H44, 4-MeOC6H45, 4-H2NC6H46, 4-F3CC6H47, 4-ClC6H48, 3-ClC6H49, 2-ClC5NH310 4-FC6H411). All resulting nickel(II) complexes have been fully characterized, in most cases including X-ray diffraction. In contrast to the work described by Matsubara and coworkers just recently on the sterically slightly more demanding [Ni(Dip2Im)2] system, we have found for the [Ni(iPr2Im)2] complexes no indication for the formation of three coordinated nickel(I) complexes.  相似文献   

10.
Reactions of manganese and zinc chloride with dimethoxyethane (DME) in the presence of (CH3)3SiCl and water resulted in [MnCl2(DME)]n (1) with a polymeric chain structure and in the molecular [ZnCl2(DME)]2 (2), respectively. The complexes 1 and 2 reacted with di(2-methoxyethyl) ether (abbreviated diglyme) in tetrahydrofuran (THF) solvent achieving binuclear [MnCl2(diglyme)]2 (3) and mononuclear [ZnCl2(diglyme)] (4), respectively. The complex [NiCl2(diglyme)]2 (5) was prepared by the reaction of nickel chloride hexahydrate, diglyme and (CH3)3SiCl in THF solvent. A distorted octahedral geometry was found for manganese and nickel ions in the complexes 1, 3 and 5. Linear chains of manganese ions linked by double chloride bridges are present in 1. Two bridging chlorides connect two manganese or nickel atoms into isostructural binuclear molecules 3 and 5, respectively. Two zinc ions in the complex 2 are in different environments, in a tetrahedral and in an octahedral one, while five-coordinate zinc ions are present in the mononuclear complexes 4.  相似文献   

11.
A series of nickel(II) complexes having the (Me-Tp)2PMA ligand ((Me-Tp)2PMA = bis(5-methyl-2-thiophenemethyl)(2-pyridylmethyl)amine) with nitrates (1), chlorides (2), and perchlorates (3) as anions were synthesized and isolated. All these complexes were successfully characterized by physicochemical methods including X-ray crystallographic analysis. In complex 1, the ligand binds in a bidentate N2 fashion, whereas in the cases of 2 and 3 the ligand binds in the tridentate N2S form. The coordination geometry around the nickel(II) atoms in these complexes is distorted octahedral.  相似文献   

12.
Group IV metallocene triphenylsiloxy chlorides, Cp2MCl(OSiPh3) (1, M=Ti; 2, M=Zr; 3, M=Hf), and cyclic organohydroborates, Cp2M(OSiPh3){(μ-H)2BC8H14} (4, M=Zr; 5, M=Hf), were synthesized and characterized. The new hafnocene chloride derivative 3 was obtained by treating Cp2HfCl2 with triphenylsilanol and piperidine. The 18-electron cyclic organohydroborates 4 and 5 were afforded by reacting 2 and 3 with K[H2BC8H14], the potassium salt of the 9-BBN dimer. Reaction of 1 with K[H2BC8H14] causes reduction of the Ti(IV) center and produces the well-known Ti(III), 17-electron, paramagnetic dimer [Cp2Ti(μ-Cl)2TiCp2] (6). Single-crystal X-ray diffraction structures of 3, 4, 5, and 6 were determined.  相似文献   

13.
Bis(silylamino)tin dichlorides 1 [X2SnCl2 with X=N(Me3Si)2 (a), N(9-BBN)SiMe3 (b), N(tBu)SiMe3 (c), and N(SiMe2CH2)2 (d)] were prepared from the reaction of two equivalents of the respective lithium amides (Li-a-d) with tin tetrachloride, SnCl4, or from the 1:1 reaction of the respective bis(amino)stannylene with SnCl4. The compounds 1 react with two equivalents of lithium alkynides LiCCR1 to give the di(1-alkynyl)-bis(silylamino)tin compounds X2Sn(CCR1)2, 2 (R1=Me), 3 (R1=tBu), and 4 (R1=SiMe3). Problems were encountered, mainly with LiCCtBu as well as with 1b, since side reactions also led to the formation of 1-alkynyl-bis(silylamino)tin chlorides 5-7 and tri(1-alkynyl)(silylamino)tin compounds 8 and 9. 1,1-Ethylboration of compounds 2-4 led to stannoles 10, 11, and in the case of propynides, also to 1,4-stannabora-2,5-cyclohexadiene derivatives 12. The molecular structure of the stannole 11b (R1=SiMe3) was determined by X-ray analysis. The reaction of 2a and d with triallylborane afforded novel heterocycles, the 1,3-stannabora-2-ethylidene-4-cyclopentenes 14. These reactions proceed via intermolecular 1,1-allylboration, followed by an intramolecular 1,2-allylboration to give 14, and a second intramolecular 1,2-allylboration leads to the bicyclic compounds 15.  相似文献   

14.
Reaction of 3-(2-pyridylmethyl)indenyl lithium (1) with LnI2(THF)2 (Ln = Sm, Yb) in THF produced the divalent organolanthanides (C5H4NCH2C9H6)2LnII(THF) (Ln = Sm (2), Yb (3)) in high yield. 1 reacts with LnCl3 (Ln = Nd, Sm, Yb) in THF to give bis(3-(2-pyridylmethyl)indenyl) lanthanide chlorides (C5H4NCH2C9H6)2LnIIICl (Ln = Nd (4), Sm (5)) and the unexpected divalent lanthanides 3 (Ln = Yb). Complexes 2-5 show more stable in air than the non-functionalized analogues. X-ray structural analyses of 2-4 were performed. 2 and 3 belong to the high symmetrical space group (Cmcm) with the same structures, they are THF-solvated 9-coordinate monomeric in the solid state, while 4 is an unsolvated 9-coordinate monomer with a trans arrangement of both the sidearms and indenyl rings in the solid state. Additionally, 2 and 3 show moderate polymerization activities for ε-caprolactone (CL).  相似文献   

15.
Triorganotin chlorides Me3SnCl and (LNC)Me2SnCl (LNC = 2-[(dimethylamino)methyl]phenyl) reacted with potassium 1′-(diphenylphosphino)-1-ferrocenecarboxylate to give the respective carboxylates, Ph2PfcCO2SnMe3 (1) and Ph2PfcCO2SnMe2(LNC) (2; fc = ferrocene-1,1′-diyl), while the analogous triphenylstannyl derivative 3 resulted by condensation of Ph3SnOH with 1′-(diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf). Compounds 1 and 2 were smoothly oxidized with hydrogen peroxide or elemental sulfur to afford the corresponding P-chalcogen derivatives (P-oxides 1a and 2a; P-sulfides 1b and 2b). All compounds were characterized by multinuclear NMR, IR and mass spectroscopy, and the solid-state structures of 1, 1a, 2, 2a and 2b were determined by single-crystal X-ray diffraction. In the crystal structures of 1 and 1a, the tin atoms were found with distorted trigonal bipyramidal coordination environments completed by the CO or PO oxygens, respectively, from adjacent molecules, which in turn resulted in the formation of infinite linear assemblies. Tin atoms in 2, 2a, and 2b were found with trigonal bipyramidal surrounding as well, though with the donor substituent LNC assuming one of the axial donor sites. Compounds 2 and 2a crystallized as stoichiometric hydrates (2·1/2H2O, 2a·H2O), in which the water molecules served as hydrogen bond donors for the polar groups (CO and PO) and thus aided the formation of closed H-bonded assemblies; the structure of 2b was essentially molecular.  相似文献   

16.
The organotin (IV) derivatives of 2-mercapto-4-methylpyrimidine (Hmpymt) R3SnL (R = Ph 1, PhCH22, n-Bu 3), R2SnClmLn (m = 1, n = 1, R = CH34, Ph 5, n-Bu 6, PhCH27; m = 0, n = 2, R = CH38, n-Bu 9, Ph 10, PhCH211) were obtained by the reaction of the organotin(IV) chlorides R3SnCl or R2SnCl2 with 2-mercapto-4-methylpyrimidine hydrochloride (HCl · Hmpymt) in 1:1 or 1:2 molar ratio. All complexes 1-11 were characterized by elemental analyses, IR, 1H, 13C and temperature-dependent 119Sn NMR spectra. Except for complexes 3 and 6, the structures of complexes 1, 2, 4, 5, 7, 8-11 were confirmed by X-ray crystallography. Including tin-nitrogen intramolecular interaction, the tin atoms of complexes 1-7 are all five-coordinated and their geometries are distorted trigonal bipyramidal. While the tin atoms of complexes 8-11 are six-coordinated and their geometries are distorted octahedral. Besides, the ligand adopts the different coordination modes to bond to tin atom between the complexes 1, 6, 7 and 2, 3, 4, 5, 8-11. Furthermore, intermolecular Sn?N or Sn?S interactions were recognized in crystal structures of complexes 4, 7 and 11, respectively.  相似文献   

17.
Using their amide (and pyrrole) groups, dipyrrinones act as hydrogen bonding receptors for carboxylic acids, as found in a large number of 10-oxo-semirubins (1-6). The latter can be synthesized readily by Friedel-Crafts coupling of 9-H dipyrrinones with half-ester acid chlorides or diacid dichlorides of α,ω-dicarboxylic acids, ranging from C2 to C10. With ω-oxo-alkanoic acid chains of C5 or ≥C5, intramolecular hydrogen bonding is observed. With acid chains <C5 hydrogen bonding is not observed. Uncharacteristically (for dipyrrinones), 10-oxo-dipyrrinone acids (1-6) and their corresponding esters (1e-6e) remain monomeric in hydrogen bond promoting solvents.  相似文献   

18.
Hydrothermal reactions of 1,10-phenanthroline (phen), 1,3-adamantanedicarboxylic acid (H2L) and lanthanide chlorides yielded six compounds: [Ln(L)(HL)(phen)] (Ln=Pr, 1; Nd, 2), [Ln(L)(HL)(phen)(H2O)] (Sm, 3; Eu, 4), [Tb(L)(HL)(phen)(H2O)]2·2H2O (5), [Er3(L)4(OH)(phen)]2 (6). Compounds 1-4 are structurally featured by one-dimensional polymeric chains; 5 hold binuclear structure constructed from eight-coordinated lanthanide center LnN2O6 of distorted bicapped trigonal prism bridged by dicarboxylate ligands; 6 shows that erbium ions are in mono and bicapped trigonal prismatic geometries, respectively, which are further connected by μ3-OH to give rise to trinuclear structure. Thermogravimetric analyses of 1, 3 and 5 were performed. Fluorescent measurements of 4 and 5 were carried out, respectively.  相似文献   

19.
Selenoether ligands, 2,2′-methylenebis(selanediyl)bis(2,1-phenylene)dimethanol (5), (2,2′-(ethane-1,2-diylbis(selanediyl))bis(2,1-phenylene))dimethanol (6) and (2-(benzylselanyl)phenyl)methanol (7) have been synthesized by reducing di-o-formylphenyl diselenide and reacting the in situ generated selenolate with dibromomethane, 1,2-dibromoethane and benzyl chloride, respectively. The ligands, bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenylselanyl)methane (8) and 1,2-bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenylselanyl)ethane (9) have been synthesized similarly from bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide using electrophiles dibromomethane and 1,2-dibromoethane, respectively. Activity of ligands 5-9 along with 2-(2-(benzylselanyl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (10) and 1-(2-(benzylselanyl)phenyl)-N,N-dimethylmethanamine (11) were examined for the Heck reaction of aryl halides with olefins. Bidentate Se,N ligand 11 was found to be the best one in the series and constitutes an efficient phosphine-free catalytic system with PdCl2. The catalytic system showed moderate activity for the coupling of activated aryl chlorides in the presence of tetra-n-butyl ammonium bromide (TBAB). Complexes [10-PdCl2] (12) and [11-PdCl2] (13) have shown marginally better activity in comparison to the in situ generated catalysts from PdCl2 and 10 and 11, respectively in the coupling of 4-bromoacetophenone with n-butylacrylate. Ligand 9 and complex 13 have been characterized by single crystal X-ray diffraction analysis.  相似文献   

20.
Treatment of cyclic ketones, e.g. 4, with tungsten hexachloride (WCl6) provided good yields of vinyl chlorides, e.g. 5, and/or gem-dichlorides. A trans-diequatorial dichloride 9 was prepared by treatment of the corresponding epoxide 8 with WCl6.  相似文献   

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