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1.
The complexes CdL4(ClO4)2 (1), CdL2(NO3)2 (2), and CdL2Cl2 (3) (L = (Me2N)3P(Se)) have been prepared and characterized by elemental analysis, conductivity measurements, IR, and multinuclear (31P, 77Se, and 113Cd) NMR spectroscopy. 31P and 77Se NMR data were informative of changes associated with complex formation. The structure of the prepared complexes was further confirmed in solution by their 113Cd NMR spectra, which show a quintuplet for the perchlorate complex and a triplet for each of the nitrate and chloride complexes due, respectively, to coupling with four and two equivalent phosphorus atoms, consistent with a four coordinate tetrahedral geometry for the cadmium center. The NMR data are discussed and compared with those reported for related complexes.  相似文献   

2.

The two octahedral complexes SnCl4·2(O)PF(NR2)2 (R = Me or Et) were prepared from reaction of SnCl4 with the ligand (R2N)2P(O)F in anhydrous CHCl3. The new adducts have been characterized by elemental analysis, IR, and multinuclear (119Sn, 31P, 19F, and 1H) NMR spectroscopy. The NMR data show that the adducts exist in solution as a mixture of cis and trans isomers with markedly different proportions. When compared with previously described hexamethylphosphoramide (HMPA) and trimethylphosphate (TMPA) analogues, our results indicate that the cis isomer is the predominant species in solution. Low temperature 31P and 119Sn NMR spectra show that the compounds partially dissociate in dichloromethane.  相似文献   

3.
Abstract

Five new complexes ZnL2(ClO4)2 (1), CdL2(ClO4)2 (2), CdL2(BF4)2 (3), CdLCl2 (4), and CdL(NO3)2 (5) [L = ((Me2N)2PSe)2NMe] have been synthesized and characterized by elemental analysis, infrared (IR) and multinuclear (31P, 77Se, and 113Cd), and nuclear magnetic resonance (NMR) spectroscopy. The 31P and 77Se NMR data showed that the title ligand is coordinated in a bidentate fashion to the metal center via its both P=Se groups. The solution structure of the cadmium complexes was further confirmed by its 113Cd NMR spectra, which displayed a quintuplet for the perchlorate complex and a triplet for each of the nitrate and chloride complexes, respectively due to coupling with four (two ligands) and two (one ligand) equivalent phosphorus nuclei, consistent with a four-coordinate tetrahedral geometry for the cadmium center. The results are discussed and compared with the corresponding oxo and thio analogues.  相似文献   

4.
The preparation and characterization of a series of octahedral complexes [SnF4L2] (L = (Me2N)3PO (1), L = (R2N)2P(O)F; R = Me (2); Et (3) or L = R2NP(O)F2; R = Me (4); Et (5)) are described. These new adducts have been characterised by multinuclear (19F, 31P and 119Sn) NMR, IR spectroscopy and elemental analysis. The NMR data particularly the 19F NMR spectra showed that the complexes exist in solution as mixtures of cis and trans isomers. The solution behaviour of the complexes studied by variable temperature NMR in the presence of excess ligand indicated that, unlike in the SnCl4 analogues, the ligand exchange at room temperature is slow for 13 and fast only for 4 and 5. The metal–ligand exchange barriers in [SnF4L2] and [SnCl4L2] systems were estimated and compared. The results indicate that in addition to the difference in the Lewis acidity between SnF4 and SnCl4 the nature of the substituents (fluorine atoms) on the phosphorus atom of the ligand can contribute considerably to the lability of the complex obtained.  相似文献   

5.
6.
Abstract

Schiff bases S-benzyl- and S-methyl-β-N-(2-hydroxyphenyl)methylene dithiocarbazate (H2L1 and H2L2, respectively) and S-benzyl- and S-methyl-β-N-(2-chlorophenyl)methylenedithiocarbazate (HL3 and HL4, respectively) were prepared. Then organotin(IV) complexes [SnPh2(L1)] (1), [SnMe2(L1)] (2), [SnPh2(L2)] (3), [SnMe2(L2)] (4), [SnPh2Cl(L3)] (5), and [SnPh2Cl(L4)] (6) were obtained from the reaction of Schiff bases with SnR2Cl2 (R = Ph and Me). The synthesized complexes have been investigated by elemental analysis and IR, 1H NMR, and 119Sn NMR spectroscopy. Spectroscopic studies show that, in complexes 1–4, the Schiff base acts as a tridentate dianionic ligand and coordinates through the thiol group, imine nitrogen, and phenolic oxygen. The coordination number of tin is five. In complexes 5 and 6, the ligand is monoanionic and unidentate, and coordinated only via the thiol group, and the azomethine nitrogen is not involved in coordination to tin. Therefore the coordination number of tin is four.

GRAPHICAL ABSTRACT   相似文献   

7.
The two octahedral complexes SnCl4 · 2(O)P(NR2)2OCH2CF3 (R = Me (1) or Et (2)) have been prepared from SnCl4 and the ligands (R2N)2P(O)OCH2CF3 in chloroform solution. Both adducts have been characterised by (31P and 119Sn) NMR, IR spectroscopy and elemental analysis. The NMR data show that the complexes exist as mixtures of cis and trans isomers in solution with the latter isomer being the predominant species. The structure of 1 has been determined by X-ray crystallography. Accordingly, the structure is centrosymmetric and the two ligands are bound trans to each other in the octahedral tin complex. DFT/B3LYP calculations show that trans configuration does indeed lead to the lowest energy species. Comparison of the structural, NMR and theoretical data of both complexes with those related to SnCl4 · 2L (L = (Me2N)3P(O) and (Me2N)2P(O)F) further supports the important effects of the nature of the substituents in the ligand on the stereochemistry of the complex formed.  相似文献   

8.
Reaction of [AuIII(C6F5)3(tht)] with RaaiR′ in dichloromethane medium leads to [AuIII(C6F5)3 (RaaiR′)] [RaaiR′=p-R-C6H4-N=N-C3H2-NN-l-R′, (1-3), R = H (a), Me (b), Cl (c) and R′= Me (1), CH2CH3 (2), CH2Ph (3), tht is tetrahydrothiophen]. The nine new complexes are characterised by ES/MS as well as FAB, IR and multinuclear NMR (1H,13C,19F) spectroscopic studies. In addition to dimensional NMR studies as1H,1H COSY and1H13C HMQC permit complete assignment of the complexes in the solution phase.  相似文献   

9.
Abstract

The reaction of SnCl4 with β-chlorovinyl aldehydes in anhydrous dichloromethane gave a series of octahedral complexes of the general formula SnCl4·2L (L = aldehyde). The adducts have been characterized in solution using multinuclear (1H, 13C, and 119Sn) NMR and IR spectroscopy. Solution NMR studies show that the complexes undergo rapid ligand dissociation at ambient temperature. Ligand exchange is slowed significantly at low temperature, such that, in most of the complexes, it is possible to identify both the cis and trans isomers with predominance of the cis form. The magnitude of the metal-ligand interaction was estimated on the basis of 119Sn NMR chemical shifts and used to classify the aldehydes studied according to their Lewis basicity.  相似文献   

10.
New cadmium(II) complexes with phosphine telluride ligands of the type CdX2(R3PTe)n [X?=?ClO4?, n?=?4: R?=?n-Bu (1), Me2?N (2), C5H10?N (3), C4H8?N (4) or OC4H8?N (5); X?=?Cl, n?=?2: R?=?n-Bu (6), Me2?N (7), C5H10?N (8), C4H8?N (9) or OC4H8?N (10)] have been synthesized and characterized by elemental analyses, IR and multinuclear (31P, 125Te, and 113Cd) NMR spectroscopy. In particular, the solution structures of these complexes were confirmed by 113Cd NMR at low temperature, which displays a quintuplet for each of the perchlorate complexes and a triplet for each of the chloride complexes due to coupling with four and two equivalent phosphorus atoms, respectively, indicating a four-coordinate tetrahedral geometry for the metal center. These multiplet features were further accompanied by one bond Te–Cd couplings, clearly showing that the ligand is coordinated to the metal through tellurium. The results are discussed and compared with those obtained for closely related phosphine chalcogenide analogs.  相似文献   

11.
Abstract

The organotin(IV) complexes, SnPh2La (1), SnMe2La (2), SnBu2La (3), SnPh2Lb (4), SnMe2Lb (5), SnPh2Lc (6), SnMe2Lc (7), and SnBu2Lc (8) were obtained by reaction of SnR 2Cl2 (R = Ph, Me, and Bu) with 1-(5-bromo-2-hydroxybenzylidene)-4-phenylthiosemicarbazide (H2La), 1-((2-hydroxynaphthalen-1-yl)methylene)-4-phenylthiosemicarbazide (H2Lb), and 1-(2-hydroxy-3-methoxybenzylidene)-4-phenylthiosemicarbazide (H2Lc). The synthesized complexes have been investigated by elemental analysis, IR, 1H NMR, and 119Sn NMR spectroscopy. The data show that the thiosemicarbazone acts as a tridentate dianionic ligand and coordinates via the thiol group, imine nitrogen, and phenolic oxygen. The coordination number of tin is 5. The in vitro antibacterial activities of the ligands and their complexes have been evaluated against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and compared with the standard antibacterial drugs.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures and tables]  相似文献   

12.
Abstract

Reactions of the salts K2SN2 and K[(NSN)R] (R = ′Bu, SiMe3 and P′Bu2) with organoelement chlorides R′R′ěl have been used to prepare four series of model sulfur diimides: R′R″E(NSN)ER″R′, ′Bu(NSN)ER″R′, Me3Si(NSN)E″R′ and tBu2P(NSN)ER″R′, respectively (E = C, Si, Ge, Sn; R′ and R″ = alkyl or aryl group). All compounds have been characterized by ′H and 13C NMR and—if possible—by 31P, 29Si and 119Sn NMR spectroscopy. The configuration (Z or E) of the substituents R and E″R′ has been assigned in several cases using tBu(NSN)tBu (1) as a reference. The E,Z assignment of 1H, 13C and 15N nuclei in 1 is based on selectively 1H-decoupled refocused INEPT 15N NMR and two-dimensional (2D) 13C/1H heteronuclear shift correlations. The sulfur diimides under study are in general fluxional in solution.  相似文献   

13.
Abstract

The synthesis of octahedral complexes [SnCl4L2] (L = R2NP(O)(OCH2CF3)(O-p-tolyl): R2N = Me2N (1), Et2N (2), CH2(CH2CH2)2N (3), and O(CH2CH2)2N (4), or L = R2NP(O)(OCH2CF3)(O-p-PhNO2): R2N = Me2N (5), Et2N (6), and O(CH2CH2)2N (7) is described. The new adducts have been characterized by multinuclear (31P, 19F, 119Sn) NMR, IR spectroscopy, and elemental analyses. The solution NMR data show the presence of a mixture of cis and trans isomers. The structure of the complexes in solution was further confirmed by 119Sn NMR spectra, which display a triplet for each isomer, indicating an octahedrally coordinated tin center. The effects of the nature of R and Ar substituents on the donor ability of the P=O group in the ligands R2NP(O)(OCH2CF3)(OAr) were investigated on the basis of 119Sn NMR chemical shifts and used to classify these ligands according to their Lewis basicity.  相似文献   

14.
Four new zinc(II) complexes of the type [ZnCl2(n-Bu3PE)2] (E=O (1), S (2), Se (3), or Te (4)) have been synthesized from zinc(II) chloride and the ligands n-Bu3PE giving yields of 56–88%. The adducts were characterized by multinuclear (31P, 13C, and 77Se) NMR, conductivity, IR spectroscopy and by X-ray analyses. Zinc complexes 14 are compriseS of two ligands coordinated to the metal center in a distorted tetrahedral arrangement. The P=E bond lengths of 1.497(7) (E=O), 2.000(4) (E=S), and 2.178(2) Å (E=Se) in these complexes are slightly elongated compared to those in the free ligand. In addition, a DFT/B3LYP theoretical study on the geometry optimization of the title ligands and their zinc complexes has been carried out in order to support and complement the experimental data and to further investigate the nature of the chalcogenide-metal interaction. The results show good agreement between the experimental and theoretical data.  相似文献   

15.
O,O-Alkylenedithiophosphates of diorganotin(IV) of the type R2Sn[SP(S)O2G]2 (R = Me, Et, n-Bu, Ph; G = CH2CMe2CH2, CMe2CMe2, CMe2CH2CHMe) have been synthesized by the reactions of diorganotin(IV) dichlorides with ammonium O,O-alkylenedithiophosphates or that of diorganotin(IV) oxides with O,O-alkylenedithiophosphoric acids in 1:2 molar ratio in benzene. These new complexes are white solids which are soluble in common organic solvents and are monomeric in refluxing benzene; and they have been characterized by elemental analysis and by different spectroscopic (IR, 1H, 13C, 31P and 119Sn NMR) studies, on the basis of which a six coordinated octahedral structure has been suggested in solution.  相似文献   

16.
Abstract

Reaction of tri-n-butyl tin(IV) chloride with the sodium salt of Schiff bases [salicylidene-2-aminopyridine (sapH), salicylidene-2-amino-4-picoline (sapicH), salicylidene-2-methyl-1-aminobenzene (o-smabH), salicylidene-4-methyl-1-aminobenzene (p-smabH), salicylidene-1- aminobenzene (sabH), salicylidene-3-nitro-1-aminobenzene (snabH)] in MeOH-C6H6 mixture in 1:1 molar ratio produced complexes of the type [Bun 3Sn(sb)] (where sb = Schiff bases). All complexes obtained were characterized by elemental analysis (C, H, N, and Sn), infrared (IR), nuclear magnetic resonance (NMR; 1H, 13C, and 119Sn), and TOF-MS spectroscopic studies. These complexes were found to be monomeric, colored viscous liquids and are soluble in polar solvents (methanol, ethanol, DMSO, and DMF). On the basis of 119Sn NMR observations, a five coordination geometry around tin(IV) atom in these complexes is proposed tentatively.  相似文献   

17.
《Polyhedron》1986,5(9):1449-1458
Three series of organotin(IV) cysteamine complexes have been prepared in which the 1,2-aminothiol may be monodentate, chelating or bridging, on the 119Sn, 15N or 13C NMR spectroscopic and other physical evidence. Triorganotin(IV) complexes [SnR3(SCH2 CH2NR′2] (R = Me, Bun or Ph; R′ = H, Me or Et) are monomeric and the aminothiol monodentate in non-coordinating solvents. Dialkyltin(IV) chloro complexes [SnR2Cl(SCH2CH2NR′2)] (R = Me, Et, Bun or Octn; R′ = H, Me or Et), however, are monomeric with chelation of the aminothiol, like the SnR2Cl complex of ethyl cysteinate, although nitrogen ligation is hindered by N,N-dialkylation. These solution properties contrast with the polymeric solid structures that are likely for [SnR2Cl(SCH2CH2NH2)] complexes with R = Me or Et, though not for R = Bun or Octn. Dialkyltin bis-cysteamine complexes [SnR2(SCH2CH2NR′2)2] (R = Me, Et, Bun or Octn; R′ = H or Et) show an intermolecular association as neat liquids and in non-coordinating solvents, increasingly with concentration, but again, nitrogen ligation is hindered by tertiary amino groups. The 15N results usefully complement those from 119Sn and 13C NMR spectroscopy.  相似文献   

18.
Two diorganotin(IV) complexes of the general formula R2Sn[Ph(O)CCH-C(Me)N-NC(O)Ph] (R=Ph, 1; R=Me, 2) have been synthesised from the corresponding diorganotin(IV) dichloride and the ligand 4-phenyl-2,4-butanedionebenzoylhydrazone(2−) (H2L), derived from benzoyl acetone and benzoyl hydrazide in methanol at room temperature in presence of triethylamine. The syntheses were performed under very mild conditions, at room temperature and without exclusion of air or moisture from the reaction vessel. Previously, rigorous conditions have been considered necessary for these species. The two compounds have been characterised by elemental analysis, IR and 1H, 13C, 15N, 119Sn NMR spectra, and their structures have been confirmed single crystal X-ray structure analysis. The central tin atom of both complexes adopts a distorted trigonal bipyramidal coordination with two ligand oxygen atoms in axial positions, the nitrogen atom of the ligand and two organic groups on tin occupying equatorial sites. 2 has crystallised with two crystallographically independent molecules in the asymmetric unit. The δ(119Sn) values for the complexes 1 and 2 are −151.5 and −146.8 ppm, respectively, thus indicating penta-coordinated tin centres.  相似文献   

19.
Equimolar reactions of BuSn(OPri)3 with diethanolamines, RN(CH2CH2 OH) 2 (abbreviated as RdeaH2, where R = H or Me), afford dimeric isopropoxo-bridged six-coordinate butyltin(IV) complexes [{Bu(η3-Rdea)Sn(μ-OPri)}2] (R = H ( 1 ), Me ( 2 )). Interactions between BuSn(OPri)3 and diethanolamines (RdeaH2) in a 1:2 molar ratio yield monomeric derivatives of the type [BuSn(Rdea)(RdeaH)] (R = H ( 3 ), R = Me ( 4 )). These homometallic complexes on 1:1 reactions with an appropriate metal alkoxide form monomeric heterobimetallic complexes of the type [BuSn (Rdea)2 {M(OR′)n}] (R = H, M = Al, R′ = Pri, n = 2 ( 5 ); R = H, M = Ti, R = Pri, n = 3 ( 6 ); R = H, M = Zr, R′ = Pri, n = 3 ( 7 ); R = Me, M = Al, R′ = Pri, n = 2 ( 8 ); R = Me, M = Ti, R′ = Pri, n = 3 ( 9 ); R = Me, M = Ge, R′ = Et, n = 3 ( 10 )). The driving force behind this work was (i) to explore the utility of homometal complexes ( 1 ) ( 4 ) in assembling a metal alkoxide fragment via a condensation reaction and (ii) to gain insights into the structures of new compounds by NMR spectral data. All of these derivatives have been characterized by elemental analysis, spectroscopic (IR, NMR; 1H, 27Al, and 119Sn) studies, and molecular weight measurements. 119Sn NMR spectral studies indicate that both the homometallic ( 3 ) and ( 4 ) and heterobimetallic ( 5 ) ( 9 ) complexes exist in a solution in an equilibrium of six- and five-coordinated tin(IV) species.  相似文献   

20.
This article describes the synthesis and characterization of several new diorganotin(IV) tetraazamacrocyclic complexes. The template condensation of anthranilic acid and diethylenetriamine with 1,2-dibromoethane or 1,3-dibromopropane in the presence of diorganotin(IV) dichlorides yielded macrocyclic complexes. The geometry and the mode of bonding of the resulting complexes were inferred from elemental analysis, UV-Vis, IR, Direct Analysis in Real Time-mass, (1H, 13C and 119Sn) NMR, and 119mSn Mössbauer spectral studies. These studies suggested that the macrocyclic ligands are tetradentate, coordinating through four nitrogens giving a skew-trapezoidal bipyramidal environment around tin in the [R2Sn(L-1)/(L-2)] (R = Me, n-Bu and Ph; H2L-1/H2L-2 = macrocyclic ligands) complexes. Thermal studies of the complexes were carried out in the temperature range 25–1000°C using thermogravimetry, derivative thermogravimetry, and differential thermal analysis techniques which provided a simple route to nanosized semi conducting SnO2 grains, identified by X-ray diffraction analysis. The particle size of the residue, obtained by pyrolysis of 2, 3, 4 and 5, determined by X-ray line broadening and transmission electron microscope were in the range ~38–48 nm and ~3–20 nm, respectively. The surface morphology of these residues was determined by scanning electron microscopy.  相似文献   

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