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1.
Reactions of Zinc and Cadmium Halides with Tris(trimethylsilyl)phosphane and Tris(trimethylsilyl)arsane ZnCl2 reacts with E(SiMe3)3 (E = P, As) in toluene in the presence of PnPr3 to give the binuclear complexes [Zn2Cl2{E(SiMe3)2}2(PnPr3)2] · C7H8 (E = P 1 , As 2 ). Therefore by the use of PiPr3 clusters consisting of ten metal atoms are obtained, [Zn10Cl12(ESiMe3)4(PiPr3)4] (E = P 3 , As 4 ). As a result of the reaction of CdBr2 with P(SiMe3)3 the compound [CdBr2{P(SiMe3)3}]2 ( 5 ) can be isolated at –40 °C. In the presence of PnPr3 CdBr2 reacts with P(SiMe3)3 forming the binuclear complex [Cd2Br2{P(SiMe3)2}2(PnPr3)2] · thf ( 6 ). The same reaction with PiPr3 yields to the cluster [Cd10Br12(PSiMe3)4{P(SiMe3)3}4] · 2 C7H8 ( 7 ). ZnI2 and CdI2 react with As(SiMe3)3 to yield the complexes [MI2{As(SiMe3)3}]2 (M = Zn 8 , Cd 9 ). In the case of CdI2 additionally the cluster [Cd10I12(AsSiMe3)4 · {As(SiMe3)3}4] · 4,5 C7H8 ( 10 ) is formed which is analogous to the compounds 3 , 4 and 7 . In the presence of [PnBu4]I 8  reacts in THF to give the ionic compound [PnBu4]2[Zn6I6(AsSiMe3)4(thf)2] · C6H6 ( 11 ).  相似文献   

2.
Syntheses, Structure Determination and Reactions of Phosphine Substituted Derivatives of Fe3(CO)93-CF)2 Photolysis of Fe3(CO)93-CF)2 1 in the presence of acetonitrile 2a or benzoenitrile 2b results in the substitution of a single carbonyl ligand by a nitrile ligand yielding Fe3(CO)8(CH3CN)(μ3-CF)2 3a and Fe3(CO)8(C6H5CN)(μ3-CF)2 3b, respectively. The acetonitrile ligand in 3a can be easily replaced by trimethyl-phosphine 4a or triphenylphosphine 4b . The monosubstituted compounds Fe3(CO)8(PR3)(μ3-CF)25, R = CH3 a, R = C6H5, b are obtained as major products besides a small amount of the disubsituted products Fe3(CO)7(PR3)23-CF)2 6. The structure of 5a has been elucidated by a single crystal X-ray structure determination. Thermal ligand substitution in 1, however, results in the formation of a mixture of mono-, disubstituted, and trisubstituted products, in which 6b is the major product for diphenylphosphine. 5a reacts with ethyne 7 forming a phosphine substituted diferra-allyl-cluster Fe3(CO)7(PR3)(μ3-CF)(μ3? CF? CH? CH) 8. The structure of one isomere of 8 has been determinated by X-ray crystallography.  相似文献   

3.
Reactions of Lithium-chlor-bis (trimethylsilyl)methane with Fluorosilanes The lithium salt of chloro-bis(trimethylsilyl)methane reacts with fluorosilanes to give monosubstituted compounds ( 1—6 ). The reaction is often accompanied by exchange of the chloro atom by hydrogen ( 3—6 ) and by formation of disubstituted products ( 7—11 ) and Cl2C(SiMe3)2. The lithiation of dichloro-bis(trimethylsilyl)methane may occur in reaction with C4H9Li ( 1—4, 6 ) or with elemental lithium ( 5 ). Butylsubstituted compounds were obtained as by products of 6 (6 a) and 10 (10 a) . The unsymetrical SiF-substituted compound 12 is formed in reaction of lithiated 2 with F2SiMe2. By absence of F2SiMe2 the lithium salt dimerises under formation of a 1, 3-disilacyclobutane and LiF.  相似文献   

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Reactions of bis(diethylamino) and dimorpholinosulfane with [Cu(H2O)6](ClO4)2 in acetonitrile and with CuCl2·2H2O in ethanol yield Cu(I) compounds and SO2. The reaction product of dimorpholinosulfane and CuCl2 in ethanol is OC4H8NSOC2H5. The reactions are discussed.  相似文献   

6.
Interaction of Borontrihalides and Tris-(trimethylsilyl)-amine According to the reaction conditions and the used halides borontrihalides BX3 (X = F, Cl, Br) and tris-(trimethylsily1)-amine, (Me3Si)3N, I, (Me ? CH3—) interact to give MeBX2, (Me3Si)2N? BMeX, (Me3Si)2N? BX2 or mixtures of these compounds; e. g. BF3, and I yield (Me3Si)2N? BF2 and Me3SiF, while BBr3 and I at 23°C form MeBBr2 and (Me3Si)2NSiMe2Br. In addition the unknown aminoboranes (Me3Si)2N? BMe2 and (Me3Si)2N? BMeBr were synthesized using a different route.  相似文献   

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The present paper deals with the behaviour of various alkyliodides towards J(OCOCF3)3 bearing a suitable functional group which can serve as an internal nucleophile. All the products found1–8 can be explained without any doubt by a typical neighbouring group effect with the bis-trifluoroacetoxyiodine anion, J(OCOCF3)2 , as an easily displaced leaving group.

F. Cech undE. Zbiral, Tetrahedron31, 605 (1975).  相似文献   

10.
Photochemical Reactions of Cyclopentadienylbis(ethene)rhodium with Benzene Derivatives During UV irradiation of [CpRh(C2H4)2] ( 1 ) (Cp = η5‐C5H5) in hexane in the presence of hexamethylbenzene the di‐ and trinuclear arene bridged complexes [(CpRh)2(μ‐η3 : η3‐C6Me6)] ( 3 ) and [(CpRh)33‐η2 : η2 : η2‐C6Me6)] ( 4 ) are formed besides known [CpRh(η4‐C6Me6)] ( 2 ). It was shown by a separate experiment that 3 besides small amounts of 4 is formed by attack of photochemically from 1 arising CpRh fragments at the free double bond of the η4‐bonded benzene ring in 2 . Irradiation of 1 in the presence of diphenyl (C12H10) affords the compounds [(CpRh)2(μ‐η3 : η3‐C12H10)] ( 5 ) and [(CpRh)33‐η2 : η2 : η2‐C12H10)] ( 6 ) as analogues of 3 and 4 , in the presence of triptycene (C20H14) only [(CpRh)2(μ‐η3 : η3‐C20H14)] ( 7 ) is obtained; the bridging in 5 , 6 , and 7 always occurs via the same six‐membered ring of the corresponding ligand system. During the photochemical reaction of 1 in the presence of styrene (C8H8) substitution of the ethene ligands by the vinyl groups with formation of [CpRh(C2H4)(η2‐C8H8)] ( 8 ) and known [CpRh(η2‐C8H8)2] ( 9 ) is observed exclusively. The new complexes were characterized analytically and spectroscopically, in the case of 3 also by X‐ray structure analysis.  相似文献   

11.
Reactions of Mixed Ligand Complexes of Nickel(0) with Carbon Dichalcogenides Decisive for the occurrence of a reaction between mixed ligand complexes of nickel(0) and carbon dichalcogenides is the HOMO-energy of the complex and the LUMO-energy of the reagent, which are reflected in the corresponding polarographic half-wave potentials. Therefore, (dipy)-Ni(COD) is substituted by SeCS, CS2 and SCO, whereas (PPh3)2Ni(C2H4) only reacts with CS2, but not with SCO. Substitution by CO2 needs substrates like Ni(PCy3)3 or Ni(PEt3)4 which have the lowest anodic waves. (PCy3)2Ni(C2H4) and (dipy)Ni(PPh3)2 effect C?S-bond breaking in SCO, and mixed carbonyls, such as (PCy3)2Ni(CO)2 or (PPh3)2Ni(CO)2, are formed. Futher products are dithiocarbonates or oligonuclear nickel sulfides which are stabilized by a phosphine. Another oligonuclear complex, (PPh3)2Ni3(CS2)2, is formed by the reaction of CS2 with surplus (PPh3)2Ni(C2H4). The function of CS2 is that of a bridging ligand. The carbon dichalcogenides are side-on (η2) coordinated in compounds like (dipy)Ni(CS2), (PPh3)Ni(CS2) and (dipy)Ni(SCO). It is always the highest electronegative heteroatom of the non symmetric ligands SeCS and SCO which does not interact with the central atom.  相似文献   

12.
Reactions of Tetraphosphorus Trichalcogenides with Alkyl Iodides Reactions of alkyl iodides RI (R = CHI2, CH2I or tert-Butyl) with P4E3 (E = S or Se) under the influence of light resulted in cleavage of the basal P3 ring. β-P4E3(I)R was formed initially, then it rearranged to the more stable α-P4E3(I)R structure. 31P NMR data of these products were measured and discussed, along with 77Se data for α- and β-P477SeSe2(I)CHI2. On reaction of P4S3 with tert-butyl iodide in CS2 or with sec-butyl iodide or iso-propyl iodide in dioxane, the new type of compounds P5S2R was observed. In this a sulfur bridge of P4S3 is replaced by a P? R group. 31P-NMR data for these compounds are reported.  相似文献   

13.
Reactions of Silylphosphines with Sulphur We report about reactions of Me2P? SiMe3 2 , MeP(SiMe3)2 3 , (Me3Si)3P 4 , P2(SiMe3)4 5 , and (Me3Si)3P7 1 with elemental sulphur. Without using a solvent 2 reacts very vigorously. The reactions with 3 and 4 show less reactivity which is even more reduced with 5 and 1 . With equivalent amounts of sulphur the reactions with 2 , 3 , 4 lead to compounds with highest content of sulphur. These compounds are Me3SiS? P(S)Me2 9 from 2 , (Me3SiS)2P(S)Me 13 from 3 and (Me3SiS)3P(S) 16 from 4 . Besides, the by-products (Me3Si)2S 8 , P2Me4 7 , and Me2P(S)? P(S)Me2 11 can be obtained. The reactions of silylphosphines in a pentane solution run much slower so that the formation of intermediates can be observed. Reaction with 2 yields Me3SiS? PMe2 6 and Me2P(S)PMe2 10 , which lead to the final products in a further reaction with sulphur. From 3 (Me3SiS)(Me3Si)PMe 14 and (Me3SiS)2PMe 12 can be obtained which react with sulphur to (Me3SiS)2P(S)Me 13. 4 leads to the intermediates (Me3SiS)(Me3Si)2P 18 , (Me3SiS)2(Me3Si)P 17 , (Me3SiS)3P 15 yielding (Me3SiS)3P(S) 16 with excess sulphur. Depending on the molar ratio (P2SiMe3)4 5 reacts to (Me3Si)2P? P(SSiMe3)(Sime3), (Me3SiS)(Me3Si)P? P(SSiMe3). (Diastereoisomer ratio 10:1), (Me3SiS)2P? P(SiMe3)2 and (Me3SiS)2P? P(SSiMe3)(Sime3). With the molar ratio 1:4 the reaction yields (Me3SiS)2P? P(SSiMe3)2 (main product), (Me3SiS)3P(S) and (Me3SiS)3P. All silylated silylphosphines tend to decompose under formation of (Me3Si)2S. (Me3Si)3P7 reacts with sulphur at 20°C (15 h) under decomposition of the P7-cage and formation of (Me3SiS)3P(S). The products of the reaction of 5 with sulphur in hexane solution (molar ratio more than 1:3) undergo readily further reactions at 60°C under cleavage of P? P bonds and splitting off (Me3Si)2S, leading to (Me3SiS)3P(S) and cage molecules like P4S3, P4S7, and P4S10 and P? S-polymers. (Me3SiS)3P(S) isi thermally unstable and decomposes to P4S10 and (Me3Si)2S. Sulphur-containing silylphosphines like (Me3SiS)P(S)Me2 react with HBr at ?78°C under formation of Me3SiBr (quantitative cleavage of the Si? S bond) and Me2P(S)SH, which reacts with HBr to produce H2S and Me2P(S)Br.  相似文献   

14.
Reactions of Antimony Pentahalides with Trichloronitromethane By reactions of SbCl5 and SbF5, respectively, with Cl3CNO2 the NO[SbCl6] and until now unknown NO[Sb2F10Cl] can be obtained; the thermal decomposition of the latter complex leads to NO[Sb2F11]. The complexes are characterized by their vibrational spectra.  相似文献   

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Reactions of 1,2-Bis(trimethylsilyl)imines with Selenium and Tellurium Halogenides The reactions of benzil-bis(trimethylsily)imine and phenanthrene-9,10-bis(trimethylsilyl)imine with SeOCl2, SeCl4 and TeCl4 are described.  相似文献   

17.
Disubstituted tetracarbonylhydridovanadium compounds (HV(CO)4L2, L2 = dppm, arphos) react with isoprene to give η3-dimethylallyl complexes of the type (η3-dimethylallyl)V(CO)3L2. The compounds have been characterized and the isomers having methyl groups in various positions of the allyl ligand identified by 1H NMR spectroscopy.  相似文献   

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20.
Reactions of Titanocene Dichloride with Cysteamine Cp2TiCl2 (Cp = η5-C5H5) reacts with HSCH2CH2NH2 (cysteamine) in boiling tetrahydrofuran to give [Cp2Ti(Cl)SCH2CH2NH3]Cl ( IV ). Even at a 1:1 reagents molar ratio, further reaction of IV takes place partially to give by cleavage of a Cp ligand the new polymer [CpTi(Cl)SCH2CH2NH]n ( V ). With 4 equivalents of cysteamine, pure V is obtained as a violet-red, air-sensitive powder which is thermally stable up to 130°C. In (CD3)2SO solution, a single 1H NMR singlet appears at δ = 6.20 ppm for the Cp protons of V . Impure V is also formed from Cp2TiCl2 with HSCH2CH2NH2 or [HSCH2CH2NH3]Cl in the presence of triethylamine as HCl acceptor, or with LiSCH2CH2NH2.  相似文献   

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