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1.
Six new arenetelluronic triorganotin esters, namely (R3Sn)4[ArTe(μ‐O)(OH)O2)]2 (Ar = Ph, R = Me: 1 , R = Ph: 2 ; Ar = 3‐Me‐Ph, R = Me: 3 , R = Ph: 4 , Ar = 3‐Cl‐Ph, R = Me: 5 , R = Ph: 6 ), were prepared by treating arenetelluronic acids with the corresponding R3SnCl (R = Me, Ph) with potassium hydroxide in methanol. All complexes were characterized by elemental analysis, FT‐IR, NMR (1H, 13C, 119Sn) spectroscopy, and X‐ray crystallography. The structural analyses indicate that these complexes are isostructural as Sn4Te2 moiety, in which the Te22‐O)2 units are situated in the center and each Te atom is coordinated with two OSnR3 groups on the side. Complexes 1 , 3 , and 5 show one‐dimensional chain and two‐dimensional network supramolecular structures by intermolecular C H···O or C H···Cl interactions. The antitumor activities of these complexes reveal that most arenetelluronic triorganotin esters have powerful antitumor activities with certain regularity.  相似文献   

2.
Interaction of metallic salts (M = Hg, Sb, and Te) with bis(triorganotin)oxide, (R3Sn)2O, where (R = C6H5, p‐CH3C6H4, and cyclo‐C6H11) at room temperature proceeded with the simultaneous cleavage of the Sn C and Sn O bonds, invariably yielding R2SnO along with other products. Thus the treatment of HgX2 (X = Cl, CN, SCN) with (R3Sn)2O resulted in the formation of polymeric diorganotin oxide R2SnO along with R3SnX and RHgX derivatives. The reaction of SbCl3 with (R3Sn)2O was found to give R2SnO, R3SnCl, and RSbCl2, whereas interaction with SbCl5 provided R2SnO, R2SnCl2, and R2SbCl3. Treatment of TeCl4 with (R3Sn)2O provided R2SnO, R3SnCl, and RTeCl3 at room temperature. At reflux temperature, reaction of PhTeCl3 with (R3Sn)2O yielded R2SnO, R3SnCl, and mixed diorganotellurium dichloride, RPhTeCl2. The course of reaction indicated the instability of Sn O Sn system proceeding via a four‐centered mechanism, providing organometallic compounds in profitable yield. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:278–283, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20547  相似文献   

3.
A series of organotin(IV) complexes of two types, [R3Sn]2(dtbu) (R = PhCH2 1 , Ph 2 , n‐Bu 3 , H2dtbu = 2,5‐dithiobiurea), [R2SnCl]2(dtbu) (R = PhCH2 4 , Ph 5 , n‐Bu 6 ) have been synthesized and characterized by elemental analysis, IR, and NMR (1H, 119Sn) spectroscopy. The structures of 2 and 6 have been determined by X‐ray crystallography. Crystal structures show that both complexes 2 and 6 are the symmetric dinuclear unit. Interestingly, supramolecular structures show that complex 2 has formed a linear chain through N H⋅⋅⋅S hydrogen bonding and 6 has formed a two‐dimensional network in perfect bc plane connected through N H⋅⋅⋅Cl hydrogen bonding and nonbonded S⋅⋅⋅S interactions. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:435–442, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20456  相似文献   

4.
Four organotin complexes with 2,2′‐bipyridine‐4,4′‐dicarboxylic acid, H2dcbp: (Ph3n)2(dcbp) 1 , [(PhCH2)3n]2(dcbp) ⋅ 2CH3OH 2 , [(Me3Sn)2(dcbp)]n 3 , [(Bu3Sn)2(dcbp)]n 4 have been synthesized. The complexes 1–4 were characterized by elemental, IR, 1H, 13C, 119n NMR, and X‐ray crystallographic analyses. Crystal structures show that complex 1 is a monomer with one ligand coordinated to two triorganotin moieties, and a 1D infinite polymeric chain generates via intermolecular C H⋅⋅⋅N hydrogen bond; complex 2 is also a monomer and forms a 2D network by intermolecular O–H⋅⋅⋅O weak interaction; both of complexes 3 and 4 form 2D network structures where 2,2′‐bipyridine‐4,4′‐dicarboxylate acts as a tetradentate ligand coordinated to trimethyltin and tri‐n‐butyltin ions, respectively. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:19–28, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20506  相似文献   

5.
Six new triorganotin 3-(salicylideneamino)benzoates ( 1a – 1c ) and 3-(4-oxo-2-penten-2-ylamino)benzoates ( 2a – 2c ), 3-(2-HOC6H4CH=N)C6H4COOSnR3, and 3-(CH3COCH=C(CH3)NH)C6H4COOSnR3 (R = Ph, a ; Cy, b ; Bu, c ) have been synthesized by one-pot reaction of 3-aminobenzoic acid, salicylaldehyde (or 2,4-pentanedione), and triorganotin hydroxide and characterized by elemental analysis, infrared, and nuclear magnetic resonance (1H, 13C, and 119Sn) spectra. The crystal structures of 1a , 1b , and 2a – 2c have been determined by the single crystal X-ray diffraction. Complexes 1a and 2a exhibit a 44-membered macrocyclic tetramer and a polymeric zigzag chain, respectively, in which tin atoms show trans-[C3SnO2] trigonal bipyramidal geometry with the axial positions being occupied by the carboxylate oxygen atom and the phenolic (or ketone) oxygen atom from another ligand. Complex 1b adopts a distorted tetrahedral geometry at tin, and there are two molecules differing in the relative orientation of the carboxylate toward the imino group. Compounds 2a ⋅CH3OH, 2b ⋅H2O, and 2c ⋅H2O are five-coordinated mononuclear adducts with one coordinated solvent molecule and display different supramolecular organizations in which there are the centrosymmetric R22(16), R42(22), and R64(34) macrocycle motifs formed by the O–H⋅⋅⋅O, N–H⋅⋅⋅O, and C–H⋅⋅⋅O hydrogen bonds. The fluorescence spectrum indicates that the complexes may be explored for potential blue luminescent materials. Compared to cisplatin, these compounds exhibit enhanced cytotoxic efficacy and can be considered as anticancer agents for further study.  相似文献   

6.
Di‐ and triorganotin(IV) carboxylates, RnSn(OCOC(R2)=CHR1)4–n (n = 2 and 3; R = Me, Et, n‐Bu, Ph; R1 = 3‐CH3O‐4‐OHC6H3, R2 = C6H5) were prepared by reacting the corresponding organotin(IV) chloride with the silver salt of the (E)‐3‐(4‐hydroxy‐3‐methoxyphenyl)‐2‐phenylpropenoic acid. The title compounds were investigated and characterized by elemental analysis, infrared (FT‐IR), multinuclear (1H, 13C, 119Sn) NMR, and mass spectrometry, and possible structures were proposed. The complexes and ligand acid ( HL ) have been evaluated in vitro against various bacteria and fungi. The results noticed during the biocidal activity screenings proved their in vitro biological potential. They were also tested for cytotoxicity.  相似文献   

7.
New series of triorganotin(IV) complexes with 4′‐nitrobenzanilide semicarbazone (L1H) and 4′‐nitrobenzanilide thiosemicarbazone (L2H) of the type [R3Sn(L)] (R = ‐CH3, ‐C6H5 and n‐C4H9) were synthesized under microwave irradiation. All the complexes were characterized by elemental analysis, conductance measurements, molecular weight determinations and spectral data, viz., IR, UV–vis, 1H, 13C and 119Sn NMR. The central tin atoms of these complexes are all five‐coordinated with trigonal bipyramidal geometry. In order to assess their growth inhibitory potency semicarbazone, thiosemicarbazone and their triorganotin(IV) complexes were tested in vitro against some pathogenic fungi and bacteria. Also the ligands and their organotin(IV) complexes were studied to assess the effects of long‐term ingestion of these compounds on fertility, body and reproductive organ weights. The biochemical analyses were also performed on blood samples and reproductive organs of male rats. The findings have been presented in this paper. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

8.
Thirty triorganotin(IV) derivatives of the type R3Sn(R′COCHCOCH2COR″) and [R3Sn]2 (R′COCHCOCHCOR″) (where R = CH3, C2H5, nC3H7, nC4H9 and C6H5 and R′ = R″ = CH3, C6H5 or R′ = C6H5, R″ = CH3) have been synthesised by the interaction of R3SnCl with mono- or disodium salt of 2, 4, 6-heptanetrione, 1-phenyl-1, 3, 5-hexanetrione and 1, 5-diphenyl-1, 3, 5-pentanetrione in 1:1 and 2:1 molar ratios, respectively. The complexes have been examined by their molecular weight, IR, PMR and elemental analyses and their tentative structures assigned. Both “Z” and “E” forms have been identified in the 1:1 complexes in equilibrium with the enol form containing five coordinate tin. The 2:1 derivatives contain one five- and other four coordinated tin(IV) except the phenyl analogue where both the tins are five coordinated.  相似文献   

9.
Four organotin complexes of the types [(Ph3Sn)(C2HN2S2)] ( 1 ), [(CH3)3Sn(C2HN2S2)]n ( 2 ), [(Bu2Sn)(C2HN2S2)2] ( 3 ), and [(Me2Sn)4(C2HN2S2)23‐O)2(C2H5O)2] ( 4 ) have been obtained by 2‐mercapto‐1,3,4‐thiadiazole and triorganotin chloride or diorganotin dichloride. All the complexes were characterized by elemental analysis, IR and NMR spectroscopy, and X‐ray diffraction analyses, which revealed that complexes 1 and 3 are mononuclear structures, complex 1 can further form a one‐dimensional (1D) helical chain, and complex 3 can further form a 22‐membered macrocycle through the intermolecular C–H·N hydrogen bond; complex 2 is a 1D infinite chain linked by intermolecular N→Sn and S→Sn bonding interactions; complex 4 is a typical ladder structure. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 00:1–8, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21046  相似文献   

10.
A series of triorganotin (4H‐1,2,4‐triazol‐4‐yl)benzoates have been synthesized by the reaction of 4‐(4H‐1,2,4‐triazol‐4‐yl)benzoic acid and 3‐(4H‐1,2,4‐triazol‐4‐yl)benzoic acid with (R3Sn)2O (R = Et, n‐Bu and Ph) or R′3SnOH (R′ = p‐tolyl and cyclohexyl). The molecular structure of tri(p‐tolyl)tin 3‐(4H‐1,2,4‐triazol‐4‐yl)benzoate determined by X‐ray crystallography displays that the tin atom adopts a five‐coordinate distorted trigonal bipyramidal geometry with the carboxyl oxygen atom and the nitrogen atom on 1‐position of triazole ring occupying the apical position. Moreover, this complex forms a polymeric chain by the intermolecular Sn–N interactions. All these complexes show good antifungal activities in vitro against Alternaria solani, Cercospora arachidicola, Gibberella zeae, Physalospora piricola, and Botrytis cinerea. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:411–417, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20566  相似文献   

11.
Thermogravimetric (TG) investigations of organotin(IV) carboxylates with the general formula RmSnL4−m (where R=CH3, C2H5, n‐C4H9, C6H5, cyclo‐C6H11, n‐C8H17, m=2, 3, and L=para‐nitrophenylethanoate anion) have been performed. Derivative thermogravimetry (DTG) and differential thermal analysis (DTA) techniques, Horowitz‐Metzger method and the fundamental thermodynamic relations are used to evaluate the thermokinetic parameters of each thermal degradation pattern. Results reveal that the thermal stability is functional to Sn C and Sn O bonds. In the case of R2SnL2, activation energy, reaction order and pre‐exponential factor associated with the bulk degradation processes increase as the alkane chain length increases. Hence, Oct2SnL2 is thermally more stable than Bu2SnL2, which in turn is more resistant to thermal dissociation than Et2SnL2. The same phenomenon is not observed for R3SnL compounds because their degradation is highly irregular. Furthermore, R2SnL2 has larger values of kinetic parameters than those of corresponding triorganotin(IV) para‐nitrophenylethanotes. Thermodynamic parameters of these compounds also reinforce the above facts.  相似文献   

12.
Reactions of bis(acetylacetonato)aluminum(III)‐di‐μ‐isopropoxo‐di‐isopropoxo aluminum(III), [(CH3COCHCOCH3)2Al(μ‐OPri)2Al(OPri)2] with aminoalcohols, (HO R NR1R2) in 1:1 and 1:2 molar ratios in refluxing anhydrous benzene yielded binuclear complexes of the types [(CH3COCHCOCH3)2Al(μ‐OPri)2Al(O R NR1R2)(OPri)] and [(CH3COCHCOCH3)2Al(μ‐OPri)2Al(O R NR1R2)2] (R   (CH2)3 , R1 = R2 = H; R =  CH2C(CH3)2 , R1 = R2 = H; R =  (CH2)2 , R1 = H, R2 =  CH3; and R   (CH2)2 , R1 = R2 = CH3), respectively. All these compounds are soluble in common organic solvents and exhibit sharp melting points. Molecular weight determinations reveal their binuclear nature in refluxing benzene. Plausible structures have been proposed on the basis of elemental analysis, molecular weight measurements, IR, NMR (1H, 13C, and 27Al), and FAB mass spectral studies. 27Al NMR spectra show the presence of both five‐ and six‐coordinated aluminum sites. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:518–522, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10184  相似文献   

13.
The diorganotin(IV) and triorganotin(IV) derivatives R2SnA (R = Me, n-Pr, n-Bu, n-Oct) and (R3Sn)2A [R = Me, Ph, cyclohexyl (Cyh); A = an anion of diphenic acid] have been prepared and characterized by elemental analysis, IR, 1H and 13C NMR spectroscopies. Tetrahedral tin forms a part of a diphenate cyclic ring in the diorganotin complexes with unidentate carboxylates, which have further been used for the synthesis of cyclic acid anhydrides. The soluble dinuclear triorganotin complexes (Me, Ph) possess symmetrically bonded carboxylates while the less soluble compound (Cyh3Sn)2A has two asymmetrically bonded carboxylates. All have a trigonal bipyramidal structure with R3Sn units remote from each other.  相似文献   

14.
Four triorganotin complexes of the types [(Ph3Sn)(C15H10FN4S)] ( 3 ), [(CH3)3Sn(C15H10FN4S)]n ( 4 ), [(Ph3Sn)(C13H9FN4S2)] ( 5 ), and [(CH3)3Sn(C13H9FN4S2)]n ( 6 ) have been obtained by Schiff base compound 1 (derived from 4‐fluorobenzaldehyde) and compound 2 (derived from thiophene‐2‐carboxadehyde) with triorganotin chloride in the presence of sodium ethoxide. All the complexes were characterized by elemental analysis, IR, and NMR spectroscopies, and X‐ray diffraction analyses, which revealed that complexes 3 and 5 are mononuclear structures, complex 4 and 6 are one‐dimensional zigzag infinite chains via N → Sn and S → Sn bonding interactions. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:583–591, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20481  相似文献   

15.
The platinum(II) mixed ligand complexes [PtCl(L1‐6)(dmso)] with six differently substituted thiourea derivatives HL, R2NC(S)NHC(O)R′ (R = Et, R′ = p‐O2N‐Ph: HL1; R = Ph, R′ = p‐O2N‐Ph: HL2; R = R′ = Ph: HL3; R = Et, R′ = o‐Cl‐Ph: HL4; R2N = EtOC(O)N(CH2CH2)2N, R′ = Ph: HL5) and Et2NC(S)N=CNH‐1‐Naph (HL6), as well as the bis(benzoylthioureato‐κO, κS)‐platinum(II) complexes [Pt(L1, 2)2] have been synthesized and characterized by elemental analysis, IR, FAB(+)‐MS, 1H‐NMR, 13C‐NMR, as well as X‐ray structure analysis ([PtCl(L1)(dmso)] and [PtCl(L3, 4)(dmso)]) and ESCA ([PtCl(L1, 2)(dmso)] and [Pt(L1, 2)2]). The mixed ligand complexes [PtCl(L)(dmso)] have a nearly square‐planar coordination at the platinum atoms. After deprotonation, the thiourea derivatives coordinate bidentately via O and S, DMSO bonds monodentately to the PtII atom via S atom in a cis arrangement with respect to the thiocarbonyl sulphur atom. The Pt—S‐bonds to the DMSO are significant shorter than those to the thiocarbonyl‐S atom. In comparison with the unsubstituted case, electron withdrawing substituents at the phenyl group of the benzoyl moiety of the thioureate (p‐NO2, o‐Cl) cause a significant elongation of the Pt—S(dmso)‐bond trans arranged to the benzoyl‐O—Pt‐bond. The ESCA data confirm the found coordination and bonding conditions. The Pt 4f7/2 electron binding energies of the complexes [PtCl(L1, 2)(dmso)] are higher than those of the bis(benzoylthioureato)‐complexes [Pt(L1, 2)2]. This may indicate a withdrawal of electron density from platinum(II) caused by the DMSO ligands.  相似文献   

16.
A series of iridium tetrahydride complexes [Ir(H)4(PSiP‐R)] bearing a tridentate pincer‐type bis(phosphino)silyl ligand ([{2‐(R2P)C6H4}2MeSi], PSiP‐R, R=Cy, iPr, or tBu) were synthesized by the reduction of [IrCl(H)(PSiP‐R)] with Me4N ⋅ BH4 under argon. The same reaction under a nitrogen atmosphere afforded a rare example of thermally stable iridium(III)–dinitrogen complexes, [Ir(H)2(N2)(PSiP‐R)]. Two isomeric dinitrogen complexes were produced, in which the PSiP ligand coordinated to the iridium center in meridional and facial orientations, respectively. Attempted substitution of the dinitrogen ligand in [Ir(H)2(N2)(PSiP‐Cy)] with PMe3 required heating at 150 °C to give the expected [Ir(H)2(PMe3)(PSiP‐Cy)] and a trigonal bipyramidal iridium(I)–dinitrogen complex, [Ir(N2)(PMe3)(PSiP‐Cy)]. The reaction of [Ir(H)4(PSiP‐Cy)] with three equivalents of 2‐norbornene (nbe) in benzene afforded [IrI(nbe)(PSiP‐Cy)] in a high yield, while a similar reaction of [Ir(H)4(PSiP‐R)] with an excess of 3,3‐dimethylbutene (tbe) in benzene gave the C H bond activation product, [IrIII(H)(Ph)(PSiP‐R)], in high yield. The oxidative addition of benzene is reversible; heating [IrIII(H)(Ph)(PSiP‐Cy)] in the presence of PPh3 in benzene resulted in reductive elimination of benzene, coordination of PPh3, and activation of the C H bond of one aromatic ring in PPh3. [IrIII(H)(Ph)(PSiP‐R)] catalyzed a direct borylation reaction of the benzene C H bond with bis(pinacolato)diboron. Molecular structures of most of the new complexes in this study were determined by a single‐crystal X‐ray analysis.  相似文献   

17.
Four triorganotin(IV) complexes with 2‐mercaptopyrimidine (HSpym) and 4‐amino‐2‐mercaptopyrimidine (HSapym) of the type, R3SnL (L= Spym, R=Ph, 1; R=PhCH2, 2; L=Sapym, R=Ph, 3; R=PhCH2, 4), were synthesized. All the complexes 1–4 have been characterized by elemental, IR, 1H NMR, and X‐ray crystallography diffraction analyses, which revealed that the structures of 1–4 are penta‐coordinated with R3Sn‐coordinated to the thiol S and heterocyclic N atoms, and the structural distortion for each is a displacement from tetragonal toward trigonal bipyramidal geometry. The complex 1 is a one‐dimensional chain complex, while compounds 3 and 4 are dimers due to the existence of N···H hydrogen bonding. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:69–75, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20068  相似文献   

18.
The diorganotin(Ⅳ) complexes of N-(3,5-dibromosalicylidene)-α-amino acid, R2Sn(2-O-3,5-Br2C6H2CH= NCHRCOO)(where R=H, Me, i-Pr, Bz; R'=n-Bu, Cy), were synthesized by the reactions of diorganotin dichlorides with in situ formed potassium salt of N-(3,5-dibromosalicylidene)-α-amino acid and characterized by elemental analysis, IR and NMR (^1H, ^13C and ^119Sn) spectra. The crystal structures of n-Bu2Sn(2-O-3,5-Br2C6H2CH= NCHRCOO)(R=i-Pr, Bz) and Cy2Sn(2-O-3,5-Br2C6H2CH=NCHRCOO)(R=Me, Bz) were determined by X-ray single crystal diffraction and showed that the tin atoms are in a distorted trigonal bipyramidal geometry to form five- and six-membered chelate rings with the tridentate ligand. Bioassay results indicated that the compounds possess better in vitro antitumour activity against three human tumour cell lines, HeLa, CoLo205 and MCF-7, than cis-platin and moderate anti-bacterial activity against two bacteria, E. coli and S. aureus.  相似文献   

19.
The reactions of diorganotin dichloride [Ph_2SnCl_2, (PhCH_2)_2-SnCl_2 or (n-Bu)_2SnCl_2] with potassium salt of 2,5-dimercapto-4-phenyl-1, 3, 4-thiodiazole gave complexes R_2Sn (S_3N_2C_8H_5)_2(4: R=Ph; 5: R=PhCH_2 and 6: R=n-Bu), respectively.Characterizations were carried out for all complexes by IR, ~1HNMR spectra and X-ray crystallography analysis. Including theSn…N interaction, the three complexes all have six-coordinateddistorted octahedral geometry. Based on the requence of stereo-chemical constraint sequence, phenyl≈benzyl>n-butyl, the lessthe effect of the stereochemical constraint of R groups, the  相似文献   

20.
Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2Ru Sn Trip] ( 1 ; IXy=1,3‐bis(2,6‐dimethylphenyl)imidazol‐2‐ylidene; Cp*=η5‐C5Me5; Trip=2,4,6‐iPr3C6H2) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β‐unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2RuSn(κ2‐O,O‐OCPhCPhO)Trip] ( 2 ) and [Cp*(IXy)(H)2RuSn(κ2‐O,C‐OCPhCHCHPh)Trip] ( 3 ), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin‐substituted ketene complex [Cp*(IXy)(H)2RuSn(OC2H5)(CHCO)Trip] ( 4 ), which is most likely a decomposition product from the putative ruthenium‐substituted stannene complex. The isolation of a ruthenium‐substituted stannene [Cp*(IXy)(H)2RuSn(Flu)Trip] ( 5 ) and stanna‐imine [Cp*(IXy)(H)2RuSn(κ2‐N,O‐NSO2C6H4Me)Trip] ( 6 ) complexes was achieved by treatment of 1 with 9‐diazofluorene and tosyl azide, respectively.  相似文献   

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