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1.
First Compound with a Six-Membered Tin(II) Transition Metal Ring – [Mn(CO)4SnCl(DMF)]3 Tin(II) chloride and dimanganese decacarbonyl were reacted in dimethyl-(DMF) at 150°C or monomethylformamide (MMF) at 120°C to yellow product solvates of the type [Mn(CO)4SnCl(D)]3 (D = DMF and MMF). Their identification in the case of the compound [Mn(CO)4SnCl(DMF)]3 was undertaken by a single crystal X-ray analysis. As result of this determination, its central molecular fragment contained a non-planar (SnMn)3 ring with the following average bond parameters: Sn? Mn bond lengths of 258.8(5) pm, endocyclic bond angle at Mn Atom of 90.5(2)° and the corresponding angle at Sn atom of 141.6(2)°. After the result of 119Sn Mößbauer spectroscopic measurements of the title substance a tin(II) oxidation state was present. The ν(CO) i.r. absorption bands and 1H n.m.r. data of both obtained products were measured for a further characterization. With view to the mechanistic pathway of the product formation, it was ascertained by separate experiments that the postulated intermediate Cl3SnMn(CO)5 and tin(II) chloride in DMF solution produced the title compound.  相似文献   

2.
A novel method of analysis of inorganic and organometallic compounds is reported. Essentially this utilizes the well-documented hydride generation technique, but in the present method the hydrides are generated from their involatile precursors (e.g. chlorides) on a GC column and separated from each other and from extraneous materials on the same GC column in a single process. Using the method, a solution of butyltin chlorides can be directly injected into a GC AA system to yield the volatile hydrides for separation, detection and quantification. To date, species analysed by this method include inorganic As(III), Me2AsOOH, inorganic Sb(III) and Sb(V), MeSnCl3, Me2SnCl2, Me3SnCl, Et2SnCl2, Et3SnCl, BuSnCl3, Bu2SnCl2, Bu3SnCl and Pr3SnCl. With the use of the internal standard Pr3SnCl and with the almost complete hydridization afforded by the technique, the procedure is shown to eliminate errors and to reduce the time involved in the analysis. The use of on-column derivatization also allows for the possibility that, in some cases, organotin hydrides reported to be found in the natural environment may, in fact, be organotin chlorides being reported as hydrides owing to inadvertent hydride production on the column. Some reports of successful gas chromatography for organotin halides could also conceivably be due to on-column hydride generation.  相似文献   

3.
Metal Complexes with Anionic Ligands of the Main Group IV Elements. IX. Reactions of Trichlorostannide and Trichlorogermide Ions with Complexes of Transition Metals in Low Oxidation States Carhonyl trichlorostannido- and carbonyl trichlorogermido-metalate complexes have been synthesized both by photochemical and thermical substitution reactions of [ECl3]? ions (E = Sn, Ge) with M(CO)6, (M = Cr, Mo, W), Fe(CO)5 Fe3(CO)12, Co2(CO)8, as well as with the metalcarbonyl derivatives (π-arene)M(CO)3, (M = Cr, Mo), (h5-C5,H5,)V(CO)4, Mn(CO)5,Cl, Co(NO)(CO)3, and Fe(NO)2,(CO)2. Mainly the bonding properties of the [ECl3]? ligands are discussed by means of i.r. spectroscopic investigations. The progress of the reactions and the necessary reaction conditions show that the nucleophilic properties oft both anions [ECl3]? are unexpectedly small. The slightly weaker hasicity of [SnCl3]? compared with [GeC13]? arreared, when both anions were reacted with Co2,(CO)8, forming the substitution product. [Co2,(CO)7,SnCl3]? and the products of a “base reaction” Cl3GcCo(CO)4, and [Co(CO)4]?.  相似文献   

4.
N-Lithiomethanesulfinicacidimide amides of the general composition MeS(NR)NRLi (II) are prepared by addition of methyllithium to sulfur diimides RNSNR (I) (R  t-Bu or SiMe3. The corresponding reaction with Me3SnNSNSnMe3 yields the N-lithio salt (Me3SnNSN)Li (III) and tetramethylstannane; addition compounds are not formed. Methatetical reactions of II with chlorostannanes, Me3SnCl or Me2SnCl2, leads to the formation of the sulfinicacidimideamidostannanes MeS(NR)NRSnMe3 (IV) and MeS(NR)NRSnClMe2 (Va), respectively.  相似文献   

5.
Preparation of Acetatolead(1V) and Acetatotin(1V) Manganese Pentacarbonyls by Acidolysis of (C6H5)4?n M[Mn(CO)5]n (M ? Sn, Pb; n = 1, 2) with Acetic Acid By acidolysis of (C6H5)4?nM[Mn(CO)5]n (M ? Sn, Pb; n = 1, 2) with acetic acid no M? Mn bonds are broken, but M? C bonds. In this reaction (CH3COO)2M[Mn(CO)5]2 is formed from (C6H5)2M[Mn(CO)5]2, and (CH3COO)3SnMn(CO)5 and (CH3COO)2C6H5PbMn(CO)5 from (C6H5)3MMn-(CO)5. (CH3COO)2C6H5SnMn(CO)5 is prepared from Cl2C6H5SnMn(CO)5 and AgCH3COO. According to IR spectroscopic data the acetato ligands of the diacetato complexes are bidentate, while in (CH3COO)3SnMn(CO)5 bi- and monodentate carboxylate groups are present. For the central atoms Sn and Pb octahedral coordination is proposed.  相似文献   

6.
Thermodynamic data have been obtained by calorimetric titration in benzene solution at 30° for reaction of organotin compounds with Lewis bases; data are reported for forty acid/base systems.Ph3SnCl forms 11 adducts of low stability with pyridine (py) or 4-methyl-pyridine (4-mepy). Ph2SnCl2, Me2SnCl2, Bu2SnCl2 and Bu2Sn(NCS)2 form simultaneously 11 and 12 adducts with py or 4-mepy and 11 adducts with 2,2′-bipyridine or 1,10-phenanthroline (phen); the enthalpies of formation of the phen adducts are similar to those of 12 adducts with 4-mepy. With BuSnCl3 and PhSnCl3 it was not possible to obtain data for each step in addition of pyridine or 4-mepy. Adduct stabilities increase with increasing chloride substitution and in the order Bu < Me < Ph; adducts of Bu2Sn(NCS)2 are more stable than those of Bu2SnCl2.Tributylphosphine does not react with Ph3SnCl but gives 11 adducts with the other tin compounds; only PhSnCl3 adds a second molecule of this base. The 11 adducts are more stable than those with heterocyclic bases. Tributylamine brings about disproportionation of the compounds R2SnX2 to R4Sn and SnX4NBu3.  相似文献   

7.
Trimethylstannyl- and Dimethylstannyl-substituted Pyrroles – Synthesis, Spectra, and Structures Monomeric trimethylstannyl pyrroles, Me3Sn? R (Me = CH3 and R = ? NC4H4, ? NC4H2Me2-2,5, ? NC4Me4-2,3,4,5, ? C4H3NMe-1), are synthesized by metathesis reactions from Me3SnCl with 1(N)- and 2(C)-lithium pyrroles, respectively. An almost similar procedure gives monomeric dimethylstannylbis(pyrroles), Me2SnR2 ( 1 a – 3 a ), from Me2SnCl2 and 1-Li-pyrrolides (1 : 2 molar ratio) in good yields. Lithiated 1,2,5-trimethylpyrrole and Me3SnCl forms the compound Me3Sn? CH2? C4H2Me(-5)NMe ( 8 ), the reaction of Me2SnCl2 with 2-lithium-1-methylpyrrole gives oligomeric [Me2Sn? C4H2NMe? ]x, ( 6 a ). The mass-, NMR, and vibrational spectra have been measured and discussed. The results of the X-ray structure determinations of Me3Sn? NC4H4 ( 1 ) and Me2Sn(? NC4Me4)2 ( 3 a ) are compared with the structures of the known dimethylmetal pyrroles of Al, Ga, and In.  相似文献   

8.
The reactions of the functional Grignard reagent Me2 NCH2CH2C(Me2)MgCl (4) with tin tetrachloride, dimethyltin dichloride, and tin (II) chloride are described. From the reactions the compounds bis(3-dimethylamino-1,1-dimethylpropyl) tin dichloride, [Me2NCH2CH2C(Me2)]2SnCl2 (5) , dimethyl(3-dimethylamino-1,1-dimethylpropyl) chlorostannane, Me2ClSnC(Me2)CH2CH2NMe2 (6) , 1,1,2,2-tetramethyl-1,2-bis(3-dimethylamino-1,1-dimethylpropyl) distannane,[Me2SnC(Me2)CH2CH2NMe2]2 (7) , 3-dimethylamino-(1,1-dimethyl)propyl tin (II) chloride, Me2NCH2CH2C(Me2)SnCl (8) , hexakis(3-dimethylamino-1,1-dimethylpropyl) cyclotristannane, {[Me2NCH2CH2C(Me2)]2Sn}3 (9a) , and the tin cluster [Me2NCH2CH2C(Me2)SnCl]3 · SnCl2 (10) have been isolated and characterized by means of multinuclear NMR and Mössbauer spectroscopy, and X-ray diffraction. 10 crystallizes in the trigonal space group P31 with the unit cell dimensions a 11.938, c 21.873 Å, V 2699.6 Å3 Z = 3. The structure was refined to a final R value of 0.064. 10 represents a tetranuclear cluster the skeleton of which is composed out of 4 Sn and a bridging Cl. Formally, the central tin atom is a SnCl+ cation stabilized by three stannylene units in a Ψ-trigonal bipyramidal environment. The tin-tin bond lengths are 288.2, 287.3 and 315.6 pm. The intramolecular Sn? N interactions amount to 242.8, 247.4 and 221.0 pm.  相似文献   

9.
The novel sixteen-electron complex [Ir(Oq)(COD)] (Oq = 8-oxyquinolate; COD = 1,5-cyclooctadiene) adds monodentate phosphines, phosphites or activated olefins irreversibly to give pentacoordinate iridium(I) complexes of the type [Ir(Oq)(COD)L] (L = PPh3, P(OPh)3, maleic anhydride or tetracyano-ethylene). Reaction of [Ir(Oq)(COD)] with some diphosphines leads to substitution products of the general formula [Ir(Oq)(diphos)] (diphos = 1,2-bis(diphenylphosphino)ethane or cis-1,2-bis(diphenylphosphino)ethylene). Carbon monoxide displaces the COD group from the complexes giving either [Ir(Oq)(CO)2] or [Ir(Oq)(CO)L], and the latter undergo oxidative addition reactions with SnCl4, Me3SiCl, Me3SnCl, MeI, allylbromide, PhCOCl, MeCOCl, Cl2, Br2, TlCl3 and HCl leading to novel iridium(III) complexes.  相似文献   

10.
The reaction of organotin chlorides with the lithium salt of 7,7,8,8-tetracyanoquinodimethane (TCNQ) or hexaalkylditins with TCNQ yield stable organotin-substituted free radicals of the types R3SnTCNQ. (R = Me, n-Pr, n-Bu) and Me2Sn(TCNQ.)2. The reaction of hexaphenylditin with TCNQ yields a (σ → π) charge transfer complex of stoichiometry (Ph3SnSnPh3)·TCNQ, whilst [Me2SnCl(terpyridyl)+](TCNQ-·) was isolated from the reaction of [Me2SnCl(terpyridlyl)+][Me2SnCl3-] and LiTCNQ. The oxidation of hexaalkylditins by tetracyanoethylene (TCNE) yields stable free radicals of the type R3SnTCNE·, but treatment with 2,3,5,6-tetrachlorobenzoquinone yields either R3SnOC6Cl4O·-p (R = Me) or R3SnOC6Cl4OSnR3-p (R = n-Bu, Ph). Tin-119 Mössbauer spectroscopy shows that the derivatives R3SnTCNQ· and R3TCNE· have trigonally-bipyramidally coordinated tin with planar [SnC3] skeletons and bridging [TCNQ·] and [TCNE·] groups forming infinite one-dimensional chain structures. Me3SnOC6Cl4O·-p was inferred to possess a similar structure but with oxy bridges forming chains with a Sn---O---Sn---O backbone. Me2Sn(TCNQ·)2 has a structure intermediate between tetrahedral and octahedral with a non-linear MeSnMe unit and anisobidentate chelation by two TCNQ groups. The TCNQ derivatives were of two types: (i) “green” or “brown”, indicative of delocalisation of the Ione electron over the cyanoquinone ligand, and (ii) a “blue” form in which spin-pairing of the Ione electron between adjacent organic groups takes place. Me3SnTCNQ· may exist in both forms depending upon the mode of preparation.  相似文献   

11.
SnCl2 as a Bridging Ligand in [{(CO)5M}2Sn(Cl)2]2? (M = Cr, Mo, W) — Synthesis, Structure, and Reactivity [{(CO)5Cr}2Sn(Cl)2]2?, 1 , may be obtained from [(CO)5Cr]2? or [(CO)5CrSnCl2 · THF] in fair yields. Alternatively, 1 is accessible by the reaction of [Cr2(CO)10]2? with SnCl2. This procedure may be extended to the synthesis of [{(CO)5M}2Sn(Cl)2]2? (M = Mo, 2 ; M = W, 3 ). The compounds 1–3 are crystallized as their alkalimetal (12-crown-4)2 or [2,2,2]cryptand salts. X-ray analyses demonstrate bridging SnCl2-moieties with M? Sn? M-angles close to 130° in each case. The relation of the bonding situation in 1–3 to the ones observed for stannylene or ?inidene”? complexes, respectively, is discussed. The transformation of 1 into the rhombododecahedral (X-ray analysis) Sn? O-cage compound [{(CO)5CrSn}63-O)43-OH)4], 4 , demonstrates the reactivity of the dianions 1–3 .  相似文献   

12.
Synthesis of mixed substituted sulfurdiimides Sulfurdiimides R? N?S?N? R ( 1 ) (R ? tBu or Me3Si) react with potassium amide via transiminating forming the potassium salts R? N?S?N)?K+ ( 2 ). Methatetical reactions of 2 with chlorides Me3SnCl or Me2SnCl2 leads to the formation of the mixed subst. sulfurdiimides R? N?S?N? SnMe3 ( 4 ) and (R? N?S?N)2SnMe2 ( 5 ), respectively.  相似文献   

13.
A dinuclear anionic complex, Bu4N[Me2SnCl(S)ClSnMe2Br], has been synthesized in chloroform solution by reacting (Me2SnS)3, Me2SnCl2, and Bu4NBr. Attempts to isolate the anionic complex using tetramethylammonium cation were unsuccessful. The anion possesses two five-coordinate tin(IV) units bridged by sulfide and bromide. X-ray diffraction study revealed the possibility of a weak Sn–Sn bond in the complex. Theoretical (DFT) studies have been carried out to analyze the nature of metal–metal interaction in the complex.  相似文献   

14.
The synthesis of novel bulky tris[dimethyl(ethyl/benzyl/p-tolyl/α-naphthyl)silylmethyl]stannanes (1-4) is described. Alkylation of SnCl4 with Me2(ethyl/p-tolyl)SiCH2MgBr (10-11) gave mainly the triorganotin chlorides [(Me2(ethyl/p-tolyl)SiCH2)]3SnCl 14 and 15, which were isolated by silica gel chromatography. Reduction of 14 and 15 with LiAlH4 in THF gave the corresponding triorganotin hydrides 1 and 2, respectively. [Me2(benzyl/α-naphthyl)SiCH2]3SnCl 16 and 17, generated by the alkylation of SnCl4 with Me2(benzyl/α-naphthyl)SiCH2MgBr 12 and 13, were inseparable from the minor product [Me2(benzyl/α-naphthyl)SiCH2]2SnCl218 and 19, respectively. Treatment of the mixtures of 16/18 and 17/19 with NaOH furnished the corresponding mixtures of stannoxanes, from which the hexakisdistannoxanes [Me2(benzyl/α-naphthyl)SiCH2]6Sn2O 20 and 22 were isolated from the minor dialkyltin oxide derivatives [Me2(benzyl/α-naphthyl)SiCH2]2SnO in good yields. Reduction of 20 and 22 with BH3 in THF gave [Me2(benzyl/α-naphthyl)SiCH2]3SnH (3 and 4), respectively in good yields. 1H, 13C, 119Sn, 29Si NMR characteristics of the newly synthesized compounds are included.  相似文献   

15.
A number of stannylene complexes with different M: Sn ratios were obtained using various metals and substituents at the tin atom. The structures of the complexes were examined. A reaction of CpMn(CO)2THF with (Ph4As)+(SnCl3)? gave the ionic complex [Ph4As]+[CpMn(CO)2SnCl3]? (I). The action of C6F5MgBr on the complex C5H5Mn(CO)(NO)SnCl3 produced C5H5Mn(CO)(NO)Sn(C6F5)3 (II). Replacement of the Cl ions in the complex [CpFe(CO)2]2SnCl2 by phenylacetylenide groups gave rise to the neutral complex [CpFe(CO)2]2Sn(C≡CPh)2 (III). A reaction of (Dppm)PtCl2 (Dppm is 1,1-bis(diphenylphosphino)methane) with SnCl2 · 2H2O in the presence of diglyme yielded the ionic complex [η3-CH3O(CH2)2O(CH2)2OCH3)SnCl]+[(η 2-Dppm)Pt(SnCl3)3]? (IV). Transmetalation in a reaction of [(Dppe)2CoCl][SnCl3] · PhBr (Dppe is 1,2-bis(diphenylphosphino)ethane) with (Dcpd)PtCl2 (Dcpd is dicyclopentadiene) in the presence of SnCl2 afforded the ionic complex [Pt(Dppe)2]3[Pt(SnCl3)5]2 (V). Structures I–V were identified by X-ray diffraction. In these structures, the formally single bonds between the atoms of transition metals M (Mn, Fe, and Pt) and Main Group heavy elements (Sn and P) having vacant d orbitals are appreciably shortened. The M-Sn bond length in complexes II and III are virtually independent of the substituents at the tin atom and the Pt-Sn bond length in complexes IV and V is virtually independent of the Pt: Sn ratio.  相似文献   

16.
Synthesis and Structures of the Dinuclear Nitrido Complexes [(Me2PhP)3(MeCN)ClRe≡N–MCl5] with M = Sn and Zr The water sensitive complexes [(Me2PhP)3(MeCN)ClRe≡N–MCl5] (M = Sn ( 1 ) und Zr ( 2 )) are obtained in dichloromethane from [ReNCl2(PMe2Ph)3] and the acetonitrile adducts of SnCl4 or ZrCl4. The compounds crystallize as dichloromethane solvate isotypically with [(Me2PhP)3(MeCN)ClRe≡N–TiCl5] · CH2Cl2 in the space group P21/n. From toluene crystallize monoclinic crystals of 1 · MeCN · C7H8. In the diamagnetic complexes 1 and 2 an anion [MCl5] coordinates to the nitrido ligand of the cationic complex [ReNCl(MeCN)(PMe2Ph)3]+. The resulting nitrido bridges Re≡N–M are almost linear and asymmetric with Re–N = 169.5 pm, Sn–N = 230.1 pm and Re–N–Sn = 164.5° for 1 and Re–N = 168.4 pm, Zr–N = 237.2 pm and Re–N–Zr = 165.6° for 2 . The phosphine ligands at the Re atom are in a meridional arrangement.  相似文献   

17.
Allyltin chlorides (or bromides) may be prepared by simple exchange reactions between tetraallyltin and the corresponding tetrahalide. Hydroboration of allylttrimethyltin yields the air-reactive borane, [Me3Sn(CH2)3]3B, which is readingly oxidised to the corresponding alcohol Me3Sn(CH2)3OH.  相似文献   

18.
Silyldiazoalkanes Me3Si(LnM)CN2 (LnM = Me3Si, Me3Ge, Me3Sn, Me3Pb; Me3As, Me3Sb, Me3Bi) have been synthesized by three different routes: (a) reactions of the Me3SiCHN2 with metal amides LnMNR1R2 of Group IVB and VB elements, using Me3SnCl as catalyst; (b) reactions of the in situ prepared organolithium compound Me3SiC(Li)N2 with organometallic chlorides Me3MCl (M = Si, Ge); (c) tincarbon bond cleavage reaction of (Me3Sn)2CN2 with Me3SiN3, affording Me3SnN3, traces of bis(trimethylsilyl)diazomethane (Me3Si)CN2, trimethylsilyl(trimethylstannyl)diazomethane Me3Si(Me3Sn)CN2 and bis(trimethylsilyl)aminoisocyanide (Me3Si)2NNC as the major reaction products. IR and NMR data (1H, 13C, 29Si, 119Sn, 207Pb) of the new heterometal-diazoalkanes are reported and discussed in comparison to relevant compounds of the organometallic diazoalkane series.  相似文献   

19.
Complexes [RC5H4Fe(CO)2]2Sn(TePh)2 (R=H, Me) containing stable heterometallic Fe−Sn−Fe fragments with two phenyltellurium groups at the tin atom were synthesized from [RC5H4Fe(CO)2]2SnCl2 (R=H, Me) and sodium phenyltelluride and their structures were established by X-ray analysis. Their chelates with tungsten tetracarbonyl, [RC5H4Fe(CO)2]2Sn(TePh)2[W(CO)4] (R=Me, H), and complexes with two Cr(CO)5 fragments or dimeric trimethylplatinum iodide were synthesized and studied by X-ray analysis. Thermal decomposition of [RC5H4Fe(CO)2]2Sn(TePh)2 complexes and their adducts with ML fragments (ML=W(CO)4, 2 Cr(CO)5, (Me3PtI)2) into inorganic tellurides of a preset mixed-metal—chalcogenide composition was studied by differential scanning calorimetry. The temperature of complete elimination of organic fragments from methylcyclopentadienyl complexes is about 100°C lower than in the case of cyclopentadienyl analogs. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1766–1772, September, 1999.  相似文献   

20.
H.J. Breunig 《Polyhedron》1984,3(6):757-758
(Me3Sn)3Sb and Fe2(CO)9 reacted to form (Me3Sn)2Fe(CO)4 in 79% yield. From (Me3E)3Sb(E = Si or Ge) and Fe2(CO)9 the complexes (Me3E)3SbFe(CO)4 were obtained  相似文献   

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