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1.
Five new organotin(IV) complexes of composition [Bz 2SnL 1] n ( 1 ), [Bz 3SnL 1H⋅H 2O] ( 2 ), [Me 2SnL 2⋅H 2O] ( 3 ), [Me 2SnL 3] ( 4 ) and [Bz 3SnL 3H] n ( 5 ) (where L 1 = (2 S )‐2‐{[( E )‐(4‐hydroxypentan‐2‐ylidene)]amino}‐4‐methylpentanoate, L 2 = ( rac )‐2‐{[( E )‐1‐(2‐hydroxyphenyl)methylidene]amino}‐4‐methylpentanoate and L 3 = (2 S )‐ or ( rac )‐2‐{[( E )‐1‐(2‐hydroxyphenyl)ethylidene]amino}‐4‐methylpentanoate) were synthesized and characterized using 1H NMR, 13C NMR, 119Sn NMR and infrared spectroscopic techniques. The crystal structure of 2 reveals a distorted trigonal‐bipyramidal geometry around the tin atom where the oxygen atoms of the carboxylate ligand and a water ligand occupy the axial positions, while the three benzyl ligands are located at the equatorial positions. On the other hand, the analogous derivative of enantiopure L 3H ( 5 ) consists of polymeric chains, in which the ligand‐bridged tin atoms adopt the same trans ‐Bz 3SnO 2 trigonal‐bipyramidal configuration and are now coordinated to a phenolic oxygen atom instead of H 2O. In 2 , the OH hydrogen of the ketoimine substituent has moved to the nearby nitrogen atom while in the salicylidene derivative 5 , the OH is located almost midway between the phenolic oxygen atom and the nitrogen atom of the CN group. For the dibenzyltin derivative 1 , a polymeric chain structure is observed as a result of a long intermolecular Sn⋅⋅⋅O bond involving the exocyclic carbonyl oxygen atom from the tridentate ligand of a neighbouring tin‐complex unit. The tin atom in this complex has distorted octahedral coordination geometry. In contrast, the racemic dimethyltin(IV) complexes 3 and 4 display discrete monomeric structures with a distorted octahedral‐ and trigonal‐bipyramidal geometry, respectively. The structures show that the coordination mode of the Schiff base ligand depends primarily on the number of bulky benzyl ligands (R) at the tin atom, as indeed found in the structures of related complexes where R = phenyl. With three bulky R groups, the tridentate chelating O,N,O coordination mode is preferred, whereas with fewer or less bulky R ligands, only the carboxylate and hydroxy groups are involved, which leads to polymers. Larvicidal efficacies of two of the new tribenzyltin(IV) complexes ( 2 and 5 ) were assessed on the second larval instar of Anopheles stephensi mosquito larvae and compared with two triphenyltin(IV) analogues, [Ph 3SnL 1H] n and [Ph 3SnL 3H] n . The results demonstrate that the compounds containing Sn–Ph ligands are more effective than those with Sn–Bz ligands. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
2.
Four different dimethyltin(IV) complexes of Schiff bases derived from 2-amino-3-hydroxypyridine and different substituted salicylaldehydes have been synthesized. The compounds, with the general formula [Me 2Sn(2-OArCHNC 5H 3NO)], where Ar = –C 6H 3(5-CH 3) [Me 2SnL 1], –C 6H 3(5-NO 2) [Me 2SnL 2], –C 6H 2(3,5-Cl 2) [Me 2SnL 3], and –C 6H 2(3,5-I 2) [Me 2SnL 4], were characterized by IR, NMR ( 1H and 13C), mass spectroscopy and elemental analysis. Me 2SnL 3 was also characterized by X-ray diffraction analysis and shows a fivefold C 2NO 2 coordination with distorted square pyramidal geometry. H 3C–Sn–CH 3 angles in the complexes were calculated using Lockhart's equations with the 1J( 117/119Sn– 13C) and 2J( 117/119Sn– 1H) values (from the 1H-NMR and 13C-NMR spectra). The in vitro antibacterial and antifungal activities of dimethyltin(IV) complexes were also investigated. 相似文献
3.
A new series of diorganotin complexes of the type R 2SnL (L 1: N‐(2‐hydroxy‐5‐chlorophenyl)‐ 3‐ethoxysalicylideneimine, R = Me, (Me 2SnL 1), R = n‐Bu, ( n‐Bu 2SnL 1), R = Ph, (Ph 2SnL 1), L 2: N‐(2‐hydroxy‐4‐nitro‐5‐chlorophenyl)‐3‐ethoxysalicylideneimine, R = Ph, Ph 2SnL 2, L 3: N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐methoxysalicylideneimine, R = Me, (Me 2SnL 3), R = n‐Bu, ( n‐Bu 2SnL 3), L 4: N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneimine, R = Me, (Me 2SnL 4), R = n‐Bu, ( n‐Bu 2SnL 4)) were synthesized and characterized by elemental analysis, infrared (IR), 1H, and 13C NMR mass spectroscopic techniques, and electrochemical measurements. Ph 2SnL 1 and Ph 2SnL 2 were also characterized by X‐ray diffraction analysis and were found to show a fivefold C 2NO 2 coordination geometry nearly halfway between a trigonal bipyramidal and distorted square pyramidal arrangement. The C Sn C angles in the complexes were calculated using Lockhart's equations with the 1J( 117/119Sn‐ 13C) and 2J( 117/119Sn‐ 1H) values from the 1H NMR and 13C NMR spectra. Biocidal activity tests against several micro‐organisms and some fungi indicate that all the complexes are mildly active against Gram (+) bacteria and the fungi, A. niger and inactive against Gram (−) bacteria. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:373–385, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20628 相似文献
4.
The complexes Me 2SnL 2 ( I ), Me 3SnL ( II ), Et 2SnL 2 ( III ), n‐Bu 2SnL 2 ( IV ), n‐Bu 3SnL ( V ), n‐Oct 2SnL 2 ( VI ), Bz 2SnL 2 ( VII ), and Ph 3SnL ( VIII ), where “L” is ( E )‐3‐(3‐fluorophenyl)‐2‐phenyl‐2‐propenoate, have been prepared and structurally characterized by means of elemental analysis, infrared, mass, and multinuclear ( 1H, 13C, 119Sn) NMR spectral techniques. The spectroscopic results showed that the geometry around the Sn atom in triorganotin(IV) derivatives is four‐coordinated in noncoordinating solvent and behaves as five‐coordinated linear polymers with bridging carboxylate groups or five‐coordinated monomers, both acquiring trans‐R 3SnO 2 geometry for Sn in the solid state. While all the diorganotin(IV) derivatives may acquire trigonal bipyramidal structures in solution due to collapse of the Sn←OCO interaction and octahedral geometries in the solid state, which have been confirmed by the X‐ray crystallographic data of the compound III . The crystal structure of Et 2SnL 2 ( III ) has been determined by X‐ray crystallography and is found skew‐trapezoidal bipyramidal, which substantiates that the ligand acts as an anisobidentate chelating agent, thus rendering the Sn atom six coordinated. The crystal is monoclinic with space group C2 1/ n. All the investigated compounds have also been screened for biocidal and cytotoxicity data. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:420–432, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20243 相似文献
5.
A series of tri‐ and di‐organotin(IV) derivatives of the types R 3SnL, R 2SnL 2 and [(R 2SnL) 2O] 2 have been synthesized by the reaction of tri‐ and di‐organotin(IV) chloride(s) with sodium cyclopropane carboxylate and sodium 3‐cyclohexylpropanoate. Based on spectroscopic evidence (IR and NMR), all the triorganotin carboxylates were found to be penta‐coordinated in the solid state (except the tricyclohexyltin derivative, which was found to be four‐coordinated) and four‐coordinated in the solution state. Attempted reaction of Me 2SnCl 2 with sodium cyclopropane carboxylate in 1:2 stoichiometry afforded a bis(dicarboxylato tetraorganodistannoxane) complex, {[Me 2Sn(cyclo‐CH 2) 2CHCOO] 2O} 2. The X‐ray diffraction of this ‘dimethyltin(IV) complex’ shows that the compound possesses a tetranuclear aggregate with one bridging bidentate and other free organic ester type monodentate carboxylate groups in which each Sn atom has a five‐coordinated geometry. These complexes were also screened for their antifungal activities. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
6.
A series of organotin(IV) thiocarboxylates have been synthesized with the general formula R 2SnL 2 and R 3SnL (R = Ph 2(I), Me 3(II), n‐Bu 3(III), Ph 3(IV), Cy 3(V), Me 2(VI), n‐Bu 2(VII), and L = piperidine‐1‐thiocarboxylic acid) in anhydrous toluene under the reflux conditions. The complexes were characterized by microanalysis, IR, 1H and 13C NMR, mass spectrometry, and XRD. NMR data revealed that thiocarboxylic acid acts as bidentate, and complexes exhibit the four‐coordinated geometry in solution state. In solid state, diorganotin complexes exhibit the hexa‐coordinated geometry whereas the triorganotin(IV) compounds show the five‐coordinated geometry. These complexes were also tested for their antimicrobial activity along with the ligand against different animals, plant pathogens, and Artemia salina. All complexes with few exceptions show high activity as compared to the ligand. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:664–674, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20380 相似文献
7.
Complexes [Me 2SnL 2 ( I ), Me 3SnL ( II ), Et 2SnL 2 ( III ), n‐Bu 2SnL 2 ( IV ), n‐Bu 3SnL ( V ), n‐Oct 2SnL 2 ( VI )], where L is ( E)‐3‐furanyl‐2‐phenyl‐2‐propenoate, have been synthesized and structurally characterized by vibrational and NMR ( 1H, 13C and 119Sn) spectroscopic techniques in combination with mass spectrometric and elemental analyses. The IR data indicate that in both the di‐ and triorganotin(IV) carboxylates the ligand moiety COO acts as a bidentate group in the solid state. The 119Sn NMR spectroscopic data, 1J[ 119Sn, 13C] and 2J[ 119Sn, 1H], coupling constants show a four‐coordinated environment around the tin atom in triorganotin(IV) and five‐coordinated in diorganotin(IV) carboxylates in noncoordinating solvents. The complexes have been screened against bacteria, fungi, and brine‐shrimp larvae to assess their biological activity. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:612–620, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20488 相似文献
8.
The reaction of 4,4′‐bipy with dimethyltin(IV) chloride iso‐thiocyanate affords the one‐dimensional (1D) coordination polymer, [Me 2Sn(NCS)Cl·(4,4′‐bipy)] n ( 1 ), whereas reaction of dimethyltin(IV) dichloride with sodium pyrazine‐2‐carboxylate in the presence of potassium iso‐thiocyanate affords the two‐dimensional (2D) coordination polymer, {[Me 2Sn(C 4H 3N 2COO) 2] 2 [Me 2Sn(NCS) 2]} n ( 2 ). Both coordination polymers were characterized by elemental analysis and infrared spectroscopy in addition to 1H and 13C NMR spectroscopy of the soluble coordination polymer ( 1 ). A single‐crystal structure determination showed that the asymmetric unit in 1 contains Me 2Sn(NCS)Cl and 4,4′‐bipy moieties and a 1D infinite rigid chain structure forms through bridging of the 4,4′‐bipy ligand between tin atoms and the geometry around the tin atom is a distorted octahedral. Coordination polymer 2 contains two distinct tin atom geometrics in which one tin atom is seven coordinate, and the other is six coordinate. The two tin atom environments are best described as a pentagonal bipyramidal in the former and distorted octahedral in the latter where the carboxylate groups bridge the two tin atoms and construct a 2D‐coordination polymer. The 119Sn NMR spectroscopy indicates the octahedral geometry of 1 retains in solution. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:699–706, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/.20736 相似文献
9.
The structure of trans‐[Cr(Me 2tn) 2Cl 2] 2ZnCl 4 (Me 2tn = 2,2‐dimethylpropane‐1,3‐diamine) was determined by a single‐crystal X‐ray diffraction study at 173 K. The analysis reveals that there are three crystallographically independent chromium(III) complex cations in the title compound. The chromium(III) atoms are coordinated by four nitrogen atoms of Me 2tn and two chlorine atoms in a trans arrangement, displaying a distorted octahedral geometry. The two six‐membered chelate rings in three complex cations are oriented in an anti chair–chair conformation with respect to each other. The Cr–N and Cr–Cl bond lengths average 2.0862(2) and 2.3112(6) Å, respectively. The ZnCl 42– have slightly distorted tetrahedral arrangement with Zn–Cl lengths and the Cl–Zn–Cl angles are influenced by hydrogen bonding. The resolved absorption maxima in the electronic d–d spectrum were fitted with a secular determinant for a quartet energy state of the d 3 configuration in a tetragonal field. It is confirmed that the nitrogen atoms of the Me 2tn ligand are strong σ donors, but the chloro ligands have weak σ‐ and π donor properties toward the chromium(III) ion. 相似文献
10.
The diorganotin(IV) complexes of methyl 2‐{4‐hydroxy‐3‐[(2‐hydroxy‐phenylimino)‐methyl]‐phenylazo}‐benzoate (H2L) were obtained by the reaction of ortho‐aminophenol, R 2SnO (R = Me, nBu, or Ph) and methyl 2‐[(E)‐(3‐formyl‐4‐hydroxy)diazenyl]benzoate (H2PL 2) in ethanol, which led to diorganotin(IV) compounds of composition [Me 2SnL] 2 ( 1 ), nBu 2SnL ( 2 ), and Ph 2SnL ( 3 ) in good yield. The 1H, 13C, and 119Sn NMR, IR, the mass spectrometry along with elemental analyses allowed establishing the structure of ligand (H2L) and compounds 1–3 . In all the three cases, 119Sn chemical shifts are indicators of five‐coordinated Sn atoms in a solution state. The crystal structures of ligand H2L and complexes 1 and 2 were determined by a single crystal X‐ray diffraction study. In the solid state, the ligand H2L exists as a keto‐enamine tautomeric form. The molecular structure of complex 1 in the solid state shows a distorted octahedral geometry around a tin atom due to additional coordination with an oxygen atom from a neighboring molecule leading to a four‐membered ring with Sn‐O···Sn‐O intermolecular coordination, leading to a dimeric species. On the other hand, complex 2 is a monomer with trigonal bipyramidal geometry surrounding the tin atom. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:457–465, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21037 相似文献
11.
Organotin(IV) dithiocarbamate complexes, RSnClL 2 and R 2SnL 2 (R = Me, Bu, Ph, and L = N-ethyl- N-phenyldithiocarbamate), have been synthesized by the reaction of mono- and disubstituted organotin(IV) with ammonium dithiocarbamate. The complexes were characterized by elemental analyses, and spectroscopic techniques ( 1H, 13C NMR and FTIR). The structures of Me 2SnL 2 and Bu 2SnL 2 were further established by single crystal X-ray diffraction technique. The crystal structure analysis showed that both complexes (Me 2SnL 2 and Bu 2SnL 2) exist as monomers. One of the dithiocarbamate ligands formed a chelate, while the other dithiocarbamate bonded to the central tin atom through one of the sulfur atoms and the second sulfur atom existed as a pendant to form distorted trigonal bipyramidal geometry. The thermal stability of all the complexes was studied using simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC). The TG-DSC results showed that Me 2SnL 2, BuSnClL 2, Bu 2SnL 2, and PhSnClL 2 displayed similar decomposition pathway via isothiocyanate intermediate, while MeSnClL 2 and Ph 2SnL 2 showed decomposition pathways different from the rest of the complexes. All the complexes resulted in SnS as the final product of the thermal decomposition process. 相似文献
12.
Organotin(IV) O-butyl carbonodithioates [Me2SnL2], [Bu2SnL2], [Ph2SnL2], [Bu3SnL], and [Ph3SnL], where L = C4H9OCS
–2
, have been successfully synthesized and characterized by FT-IR, 1H and 13C NMR, and single crystal X-ray analysis. The ligand coordinates to the tin atom via the carbonodithioate group. According to the X-ray diffraction data, the tin atom in [Me2SnL2] has distorted tetrahedral geometry. The synthesized compounds were screened in vitro for antibacterial, antifungal, antileishmanial, cytotoxic, and protein kinase inhibitory activities. The complexes [Bu3SnL] and [Ph3SnL] exhibited the highest anti-leishmanial activity that exceeded the activity of the reference drug amphotericin B, probably by blocking the function of parasitic mitochondria due to which it restricts further growth of the organisms. The ligand and the complexes have been shown to bind to DNA via intercalative interactions resulting in hypochromic effect with a minor red shift as confirmed by UV-Vis spectroscopic studies. 相似文献
13.
Complexes of L ‐methionyl‐L ‐histidine (H 2MetHis) with R 2Sn(IV) ions (R = Me, nBu, Ph) have been synthesized. The crystal and molecular structures of Me 2SnMetHis·0.5MeOH have been determined by X‐ray diffraction. The title compound contains two crystallographically independent molecular units possessing the same trigonal‐bipyramidal geometry at tin, each dimethyltin(IV) moiety being coordinated by the terminal amino nitrogen, deprotonated peptide nitrogen and terminal carboxylate group, neither the imidazole nor thioether groups being involved in bonding. IR spectroscopy was used to probe the structure of the complexes in the solid state, and the structure in solution (CD 3OD) was assessed by 1H and 13C NMR. Me 2Sn(IV)dipeptide complexes appear to be undissociated and to retain a pentacoordinated structure. Rotamer population of C‐terminal histidine was determined by analysis of vicinal coupling constants and side‐chain orientations have been interpreted with a view to potential applications of the compounds as recognition agents. Biological activity was tested on Ascidian embryos of Ciona intestinalis at different stages of development. Copyright © 2000 John Wiley & Sons, Ltd. 相似文献
14.
Four new triorganotin(IV) complexes: Me 3SnL 1SnMe 3 ( 1), Ph 3SnL 1SnPh 3 ( 2), [Me 3SnL 2] n ( 3), Ph 3SnL 2SnPh 3 ( 4) have been synthesized from 6-anilino-1,3,5-triazine-2,4-dithiol (L 1H 2) and 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (L 2H 2). All were characterized by elemental analyses, IR and NMR spectra and X-ray diffraction analyses. Crystal structures show that 1, 2 and 4 are monomers with one ligand coordinated to two triorganotin moieties; complex 3 is a helical chain. Significant C–H ··· π, N–H ··· π interactions and intermolecular hydrogen bonds stabilize these structures. 相似文献
15.
Tri‐ and diorganotin(IV) derivatives of non‐steroidal anti‐inflammatory drug sulindac ( Sul ), coordinated with carboxylate oxygen, namely C 23H 25FO 3SSn ( 1 ), C 38H 31FO 3SSn ( 2 ), C 32H 43FO 3SSn ( 3 ), C 52H 42F 2O 6S 2Sn ( 4 ), C 44H 44S 2Cl 2O 6F 2Sn 2 ( 5 ), C 48H 50F 2O 6S 2Sn ( 6 ) and C 56H 66F 2O 6S 2Sn ( 7 ), have been synthesized and characterized using analytical and spectroscopic (IR, 1H NMR, 13C NMR, 119Sn NMR and ESI‐MS) techniques. Optimized geometry and electronic structures of the complexes obtained from density functional theory calculations indicate that complexes 1 , 2 , 3 and 7 are tetra‐coordinated with monodentate carboxylates, 4 and 6 are hexa‐coordinated with highly distorted octahedral geometry, whereas 5 is penta‐coordinated with distorted trigonal bipyramidal geometry. Probable mode of DNA binding with ligand ( Sul ) and complexes 1 – 7 has been revealed via various biophysical techniques (UV–visible spectroscopy, fluorometry and circular dichroism). Intrinsic binding constants ( K b) obtained from UV–visible spectroscopy for Sul and complexes 1 – 7 are 3.69 × 10 4, and 7.3 × 10 3, 1.14 × 10 4, 1.47 × 10 4, 1.55 × 10 4, 1.49 × 10 4, 2.02 × 10 4, 1.17 × 10 4 M −1, respectively. The quenching constants ( K sv) using fluorometric titrations, calculated from competitive binding of ethidium bromide versus Sul /complexes with calf thymus DNA, also correspond to the above results. Circular dichroism spectral patterns of calf thymus DNA with Sul and complexes 1 – 7 have also been investigated. All the results reveal that the complexes bind with DNA through partial intercalative mode. pBr322 plasmid fragmentation has also been studied using gel electrophoresis, which shows the fragmentation of circular DNA by an increase in nicked form and also by the appearance of linear form with increasing concentration of drug or complexes. 相似文献
16.
Transition metal complexes of type M(L) 2(H 2O) x were synthesized, where L is deprotonated Schiff base 2,4‐dihalo‐6‐(substituted thiazol‐2‐ylimino)methylphenol derived from the condensation of aminothiazole or its derivatives with 2‐hydroxy‐3‐halobenzaldehyde and M = Co 2+, Ni 2+, Cu 2+ and Zn 2+ ( x = 0 for Cu 2+ and Zn 2+; x = 2 for Co 2+ and Ni 2+). The synthesized Schiff bases and their metal complexes were thoroughly characterized using infrared, 1H NMR, electronic and electron paramagnetic resonance spectroscopies, elemental analysis, molar conductance and magnetic susceptibility measurements, thermogravimetric analysis and scanning electron microscopy. The results reveal that the bidentate ligands form complexes having octahedral geometry around Co 2+ and Ni 2+ metal ions while the geometry around Cu 2+ and Zn 2+ metal ions is four‐coordinated. The geometries of newly synthesized Schiff bases and their metal complexes were fully optimized in Gaussian 09 using 6–31 + g(d,p) basis set. Fluorescence quenching data reveal that Zn(II) and Cu(II) complexes bind more strongly to bovine serum albumin in comparison to Co(II) and Ni(II) complexes. The ligands and their complexes were evaluated for in vitro antibacterial activity against Escherichia coli ATCC 25922 (Gram negative) and Staphylococcus aureus ATCC 29213 (Gram positive) and cytotoxicity against lever hepatocellular cell line HepG2. 相似文献
17.
A novel naphthalenediol‐based bis(salamo)‐type tetraoxime compound (H 4L) was designed and synthesized. Two new supramolecular complexes, [Cu 3(L)( μ‐OAc) 2] and [Co 3(L)( μ‐OAc) 2(MeOH) 2]·4CHCl 3 were synthesized by the reaction of H 4L with Cu(II) acetate dihydrate and Co(II) acetate dihydrate, respectively, and were characterized by elemental analyses and X‐ray crystallography. In the Cu(II) complex, Cu1 and Cu2 atoms located in the N 2O 2 sites, and are both penta‐coordinated, and Cu3 atom is also penta‐coordinated by five oxygen atoms. All the three Cu(II) atoms have geometries of slightly distorted tetragonal pyramid. In the Co(II) complex, Co1 and Co3 atoms located in the N 2O 2 sites, and are both penta‐coordinated with geometries of slightly distorted triangular bipyramid and distorted tetragonal pyramid, respectively, while Co2 atom is hexa‐coordinated by six oxygen atoms with a geometry of slightly distorted octahedron. These self‐assembling complexes form different dimensional supramolecular structures through inter‐ and intra‐molecular hydrogen bonds. The coordination bond cleavages of the two complexes have occurred upon the addition of the H +, and have reformed again via the neutralization effect of the OH ?. The changes of the two complexes response to the H +/OH ? have observed in the UV–Vis and 1H NMR spectra. 相似文献
18.
Diorganotin (IV) complexes SnR 2X 2 (R = Me, Ph; X = Cl, NCS) form a series of versatile complexes when react with bidentate substituted pyridyl ligands. The reaction of dimethyltin dichloride with 5,5′‐dimethyl‐2,2′‐bipyridine (5,5′‐Me 2bpy) resulted in the formation of [SnMe 2Cl 2(5,5′‐Me 2bpy)] ( 1 ). Moreover, the reaction of SnMe 2(NSC) 2 with 4,4′‐di‐ tert‐butyl‐2,2′‐bipyridine (bu 2bpy), 1,10‐phenanthroline (phen) and 4,7‐diphenyl‐1,10‐phenanthroline (bphen) affords the hexa‐coordinated complexes [SnMe 2(NCS) 2(bu 2bpy)] ( 2 ), [SnMe 2(NCS) 2(phen)] ( 3 ) and [SnMe 2(NCS) 2(bphen)] ( 4 ), respectively. The resulting complexes have been characterized using elemental analysis, IR, multinuclear NMR ( 1H, 13C, 119Sn) and DEPT‐135 ° NMR spectroscopy. On the other hand, the reaction of diphenyltin dichloride with 2,2′‐biquinoline (biq) and 4,7‐phenantroline (4,7‐phen) led to the formation of polymeric complexes of [SnPh 2Cl 2(4,7‐phen)] n ( 5 ) and [SnPh 2Cl 2(biq)] n ( 6 ). The NMR spectra, however, reveal the ligand lability in solution and suggest a coordination number of 5 . The X‐ray crystal structures of complexes [SnMe 2Cl 2(5,5′‐Me 2bpy)] ( 1 ), [SnMe 2(NCS) 2(bu 2bpy)] ( 2 ) and [SnMe 2(NCS) 2(bphen)] ( 4 ) have been determined which reveal that the geometry around the tin atom is distorted octahedral with trans‐[SnMe 2] configuration. Interestingly, the crystal structure of (H 2biq) 2[SnPh 2Cl 4]?2CHCl 3 ( 7 ) was characterized by X‐ray crystallography from a chloroform solution of [SnPh 2Cl 2(biq)] n ( 6 ) indicating the formation of doubly protonated [H 2biq] + and [Ph 2SnCl 4] 2? which are stabilized by a network of hydrogen bonds with a feature of trans‐[SnPh 2]. The 3D Hirshfeld surface analysis and 2D fingerprint maps were used for quantitative mapping out of the intermolecular interactions for 1 , 2 , 4 and 7 which show the presence of π‐π and hydrogen bonding interactions which are associated between donor and acceptor atoms (N, S, Cl) in the solid state. 相似文献
19.
Tin(IV) complexes of the series of dianionic terdentate Schiff bases N‐[(2‐pyrroyl)methylidene]‐N′‐tosylbenzene‐1,2‐diamine, (H 2L 1), N‐[(2‐hydroxyphenyl)methylidene]‐N′‐tosylbenzene‐1,2‐diamine (H 2L 2) and some R substituted 2‐{[(2‐hydroxyphenyl)imino]methyl}phenols [R = H (H 2L 3), 4,6‐(OCH 3) 2 (H 2L 4), 3‐(OC 2H 5) (H 2L 5) and 3,5‐Br 2 (H 2L 6)] have been synthesized. The compounds were obtained by the electrochemical oxidation of a tin anode in a cell containing an acetonitrile solution of the corresponding ligand. The complex [SnL 12] was also obtained by reaction of SnCl 2·2H 2O and H 2L 1 in methanol in the presence of triethylamine. The crystal structure of the ligand [H 2L 6] and the complexes [SnL 12] (1) , [SnL 22] (2) , [SnL 32] (3) and [SnL 62] (6) were determined by X‐ray diffraction. In the complexes, the tin atom is in an octahedral environment coordinated by two dianionic terdentate ligands. Spectroscopic data for the complexes (IR, 1H and 119Sn NMR and mass spectra) are discussed and related to structural information. 相似文献
20.
The diorganotin(IV) compounds, [Me 2SnL 2(OH 2)] 2 ( 1), [ nBu 2SnL 2(OH 2)] 2 ( 2), [ nBu 2SnL 1] 3 · 0.5C 3H 6O ( 3), [ nBu 2SnL 3] 3 · 0.5C 6H 6 ( 4) and [Ph 2SnL 3] n · 0.5C 6H 6 ( 5) (L = carboxylic acid residue, i.e., 2-{[( E)-1-(2-oxyaryl)alkylidene]amino}acetate), were synthesized by treating the appropriate diorganotin(IV) dichloride with the potassium salt of the ligand in anhydrous methanol.The reaction of Ph 2SnL 2 (L = 2-{[( E)-1-(2-oxyphenyl)ethylidene]amino}acetate) with 1,10-phenanthroline (Phen) yielded a 1:1 adduct of composition, [Ph 2SnL 2(Phen)] ( 6).The crystal structures of 1- 6 were determined.The crystal of 1 is composed of centrosymmetric dimers of the basic Me 2SnL 2(OH 2) moiety, where the two Sn-centres are linked by two asymmetric Sn-O?Sn bridges involving the carboxylic acid O atom of the ligand and a long Sn?O distance of 3.174(2) Å.The dimers are further linked into columns by hydrogen bonds.The coordination geometry about the Sn atom is a distorted pentagonal bipyramid with the two methyl groups in axial positions.The structure of 2 is similar.The same Sn atom coordination geometry is observed in compound 3, which is a cyclic trinuclear[ nBu 2SnL 1] 3 compound. Each Sn atom is coordinated by the phenoxide O atom, one carboxylate O atom and the imino N atom from one ligand and both the exo- and endo-carboxylate O atoms (mean Sn-O( exo): 2.35 Å; Sn-O( endo): 2.96 Å) from an adjacent ligand to form the equatorial plane, while the two butyl groups occupy axial positions. Compound 4 was found to crystallize in two polymorphic forms. The Sn-complex in both forms has a trinuclear [ nBu 2SnL 3] 3 structural motif similar to that found in 3. In compound 5, distorted trigonal bipyramidal Ph 2SnL 3 units are linked into polymeric cis-bridged chains by a weak Sn?O interaction (3.491(2) Å) involving the exocyclic O atom of the tridentate ligand of a neighboring Sn-complex unit. This interaction completes a highly distorted octahedron about the Sn atom, where the weakly coordinated exocyclic O atom and one phenyl group are trans to one another. In contrast, a monomeric distorted pentagonal bipyramidal geometry is found for adduct 6 where the Sn-phenyl groups occupy the axial positions. The solution and solid-state structures are compared by using 119Sn NMR chemical shift data. Compounds 1- 6 were also studied using ESI-MS and their positive- and negative-ions mass fragmentation patterns are discussed. 相似文献
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