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1.
The first triorganotin(IV) pentacyanopropenides, [R3Sn(H2O)2][C3(CN)5] (R = Me ( 2 ), nBu ( 3 ), Ph ( 4 ) were prepared by treatment of Ag[C3(CN)5] ( 1 ) with equimolar amounts of R3SnCl in reagent grade THF. In a similar manner, dark red [R3Sn(H2O)2][N{C(CN)C(CN)2}2] ( 6 ) containing the hexacyanoazapentadienyl anion was prepared in 55 % yield. The molecular structure of [Ph3Sn(H2O)2][C3(CN)5] ( 4 ) was determined by X‐ray diffraction. The crystal structure consists of separated trigonal‐bipyramidal [Ph3Sn(H2O)2]+ cations and nearly planar [C3(CN)5] anions which are linked through O–H ··· N hydrogen bonds to give a three‐dimensional network.  相似文献   

2.
A series of diorganotin bisxanthate compounds, [R2Sn(S2COR′)2] (R=Me, Et, nBu, tBu, and Ph; R′?Et, iPr and cHex) have been prepared and characterized by spectroscopic methods (IR, NMR and FAB MS). The xanthate ligands chelate the R2Sn moieties forming disparate Sn–S bonds leading to skew-trapezoidal biypramidal tin atom geometries. The crystal structure of a representative compound, [Ph2Sn(S2COEt)2], confirms the spectroscopic results and shows the tin atom to be coordinated by two asymmetrically chelating xanthate ligands [Sn–S(1) 2.486(1), Sn–S(2) 3.052(1) Å and Sn–S(3) 2.484(1), Sn–S(4) 3.220(1) Å] with the two phenyl substituents lying over the weaker Sn–S interactions so that C–Sn–C is 126.5(1)°. Crystal data for [Ph2Sn(S2COEt)2]: monoclinic space group P21/n: a=9.645(1), b=23.723(3), c=9.798(2) Å, ß=100.23(1)°, V=2206.2 Å3, Z=4; 2708 data refined to final R 0.023. A selection of these compounds has been evaluated for activity against the L1210 mouse leukaemia cell line.  相似文献   

3.
The reaction of Ph3SnCl, (R4N)2[Mo6O19] and (R4N)OH in a molar ratio of 6:1:10 leads to the formation of (R4N)[(Ph3Sn)MoO4] (R = nPr ( 1 ), nBu ( 2 )). Compounds 1· CH3CN and 2 have been charactarized by IR spectroscopy and single crystal X‐ray diffraction. 1· CH3CN forms orthorhombic crystals, space group P212121 with a = 1339.9(2), b = 1508.9(2), c = 1733.2(3) pm. 2 crystallizes in the monoclinic space group P21 with a = 1342.6(2), b = 2280.3(4), c = 1344.0(2) pm, β = 118.34(1). Both compounds 1 and 2 consist of isolated R4N+ cations and polymeric $\rm^{1}_{\infty}$ [(Ph3Sn)MoO4] chains with an alternating arrangement of Ph3Sn+ and MoO42– groups. Treatment of (Ph3Sn)2MoO4 with bis(ethylenediamine)copper(II) succinate yields [Cu(en)2(Ph3Sn)2(MoO4)2] ( 3 ). The zinc derivative [Zn(en)2(Ph3Sn)2(MoO4)2] ( 4 ) is obtained similarly by reaction of (Ph3Sn)2MoO4 with bis(ethylenediamine)zinc(II) formiate. Compounds 3· 2DMF · EtOH and 4· 2DMF · EtOH crystallize in the monoclinic space group P21/n with a = 1998.0(2), b = 1313.3(1), c = 2181.6(2) pm, β = 90.97(1)° for 3 and a = 2015.4(1), b = 1316.7(1), c = 2157.0(1) pm, β = 90.40(1)° for 4 . Like in the cases of 1 and 2, polymeric $\rm^{1}_{\infty}$ [(Ph3Sn)MoO4] chains are observed. The [M(en)2]2+ units (M = Cu, Zn) act as linkers between the $\rm^{1}_{\infty}$ [(Ph3Sn)MoO4] chains to give 2D layer structures with (6, 3) net topology.  相似文献   

4.
Summary Aminoalkanesulphonic acids H2N(CH2) n SO3H, (n = 1, 2 or 3) react with phosphonium salts [R2P(CH2OH)2]Cl (R = Ph or Cy, Cy = cyclohexyl) in the presence of Et3N to give the sulphonated aminomethylphosphines [Et3NH] [(R2PCH2)2N(CH2) n SO3] (R = Ph, n = 1, 2 or 3; R = Cy, n = 1). The single crystal X-ray structure of [Et3NH] [(Ph2PCH2)2N(CH2)2SO3] has been determined. Some NiII, PdII, PtII and RhI complexes of the phosphines have been prepared.  相似文献   

5.
Stannylation Experiments with NH-functional Aminoiminophosphoranes. Synthesis and Structure of the Tricyclic Stannaphosphazenes [Me2Sn(tBu2PN)NH]2 and [nBu2Sn(Ph2PN)2NH]2 Aminoiminophosphoranes tBu2P(NH)NH2 ( 1 ) and (H2NPPh2)N(Ph2PNH) ( 2 ) react with diaminostannanes R2Sn(NEt2)2 by cyclocondensation to give cyclostannaphosphazenes [Me2Sn(tBu2PN)NH]2 ( 3 ) and [R2Sn(Ph2PN)2NH]2 ( 4 a , b ) ( a : R = Me, b : R = nBu). With 2 and Me3SnNEt2 the ring compound Me2Sn(Ph2PN)2NSnMe3 ( 5 ) besides Me4Sn is formed by per-N-stannylation and Sn-methyl group transfer. The crystal structures of 3 and 4 b were determined by X-ray structure analysis. 3 forms a planar heterotricyclus containing three four-membered rings with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1). 4 b consists of a tricyclic molecule with two puckered six-membered rings and one planar four membered tin-nitrogen ring with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1).  相似文献   

6.
The ligands [Ph2P(O)NP(E)Ph2] (E=S I; E=Se II) can readily be complexed to a range of palladium(II) starting materials affording new six-membered Pd–O–P–N–P–E palladacycles. Hence ligand substitution reaction of the chloride complexes [PdCl2(bipy)] (bipy=2,2′-bipyridine), [{Pd(μ-Cl)(L–L)}2] (HL–L=C9H13N or C12H13N), [{Pd(μ-Cl)Cl(PMe2Ph)}2] or [PdCl2(PR3)2] [PR3=PPh3; 2PR3=Ph2PCH2CH2PPh2or cis-Ph2PCH=CHPPh2] with either I (or II) in thf or CH3OH gave [Pd{Ph2P(O)NP(E)Ph2-O,E}(bipy)]PF6, [Pd{Ph2P(O)NP(E)Ph2-O,E}(L–L)], [Pd{Ph2P(O)NP(E)Ph2-O,E}Cl(PMe2Ph)] or [Pd{Ph2P(O)NP(E)Ph2-O,E} (PR3)2]PF6 in good yields. All compounds described have been characterised by a combination of multinuclear NMR [31 P{1 H} and 1 H] and IR spectroscopy and microanalysis. The molecular structures of five complexes containing the selenium ligand II have been determined by single-crystal X-ray crystallography. Three different ring conformations were observed, a pseudo-butterfly, hinge and in the case of all three PR3 complexes, pseudo-boat conformations. Within the Pd–O–P–N–P–Se rings there is evidence for π-electron delocalisation.  相似文献   

7.
Four 1:1, two-component salts combining the [Ni(dmit)2] anion (dmit2− = 2-thioxo-1,3-dithiole-4,5-dithiolato) and chiral stilbazolium-based countercations (HPMS+ = 4′-[2-(hydroxymethyl)pyrrolidinyl]-1-methylstilbazolium and MPMS+ = 4′-[2-(methoxy-methyl)pyrrolidinyl]-1-methylstilbazolium), or chiral ferrocenyl-based countercations (2+ = (E)-1-((R)-2-methylferrocenyl)-2-(1-methyl-4-pyridiniumyl)ethene; 3+ = (E)-1-((S)-2-trimethylsilylferrocenyl)-2-(1-methyl-4-pyridiniumyl)ethene) were prepared. Semiconducting behaviour (2·10−4 S·cm−1 measured on compressed pellets for [Ni(dmit)2] (MPMS), for example) is secured by the presence of the [Ni(dmit)2] anions. The chiral nature of the countercations ensures non-centrosymmetry of the structures (space group P1 for [Ni(dmit)2](2) and [Ni(dmit)2](3), for example). A ubiquitous antiparallel arrangement of the cations, which are thus packed in a pseudo-centrosymmetrical environment, results in almost vanishing second-order susceptibilities χ(2), and therefore zero efficiencies in second harmonic generation.  相似文献   

8.
Two novel lithium compounds containing either the phosphorus-chalcogenide anions [Ph 2 PS]? or [Cy 2 PS 2 ]? were isolated as decomposition products in the attempted formation of phospha(V)guanidinate anions. Lithium diphenylthiophosphinite was structurally characterized as the dimeric TMEDA adduct [Li(Ph 2 PS)(TMEDA)] 2 (1), in which a rare example of the κ 1 -S bonding mode was observed for the anion. The dicyclohexyldithiophosphinate anion was incorporated into an aggregated structure with molecular formula [Li 5 (Cy 2 PS 2 ) 4 (OH)] 2 (2). DFT calculations were performed on the isolated [R 2 PS]? and [R 2 PS 2 ]? anions (R = Ph, Cy), indicating delocalization of electron density into the P-S bonds for each model, in agreement with bond-lengths taken from crystallographic data.  相似文献   

9.
Phenylmercuric acetate, triphenyltin chloride and dibutyltin chloride react with alkali‐metal or ammonium salts of some 1,1‐ and 1,2‐dithio ligands in appropriate molar ratios to yield a series of organometallic dithio complexes of the type [PhHgX] (X = butylxanthate (Buxant), cyclohexylxanthate (Cyxant), benzylxanthate (Bzxant) or pyrrolidin‐1‐yldithiocarbamate (Pdtc); [(PhHg)2X] (X = isomaleonitriledithiolate (i‐MNT2−) or 1‐ethoxycarbonyl‐1‐cyanoethylene‐2,2‐dithiolate (ecda2−); Ph3SnX (X = Buxant or Pdtc); [(Ph3Sn)2(i‐MNT)] and [Bu2SnMNT] (MNT2− = maleonitriledithiolate). These complexes have been characterized by elemental analysis, molar conductance measurements, IR, FT‐Raman, 1H and 13C NMR and fast atom bombardment (FAB) mass spectra. Cyclic dimeric structures for phenylmercuryxanthates and monomeric structures for the remaining complexes are suggested. Antibacterial activities of the complexes and parent ligands have been screened against some well‐known pathogenic bacteria. Organomercury dithiolates have been found to be more potential antibacterial than organotin complexes. Copyright © 2000 John Wiley & Sons, Ltd.  相似文献   

10.
Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

11.
The title compounds are salts of the general form (Q+)2[Zn(dmit)2]2?, where dmit corresponds to the ligand (C3S5)? present in both and Q+ to the counter‐cations (nBu4N)+ [or C16H36N+] and (Ph4As)+ [or C24H20As+], respectively. In the first case, Zn is in the 4e special positions of space group C2/c and hence the [Zn(dmit)2]2? dianion possesses twofold axial crystallographic symmetry. Including these, there are now 11 known examples of [Zn(dmit)2]2? or its analogues, with O replacing the exocyclic thione S, and [Zn(dmio)2]2? dianions in nine structures with various Q. Comparison of these reveals a remarkable variation in details of the conformation which the dianion may adopt in terms of Zn coordination, equivalence of the Zn—S bond lengths, displacement of Zn from the plane of the ligand and overall dianion shape.  相似文献   

12.
The compound [K([2.2.2]crypt)]Cs7[Sn9]2(en)3 ( 1 ) was synthesized from an alloy of formal composition KCs2Sn9 by dissolving in ethylenediamine (en) followed by the addition of [2.2.2]crypt and toluene. 1 crystallizes in the orthorhombic space group Pcca with a = 45.38(2), b = 9.092(4), c = 18.459(8) Å, and Z = 4. The structure consists of Cs7[Sn9]2 layers which contain [Sn9]4– anions and Cs+ cations. The layers are separated by [K([2.2.2]crypt)]+ units. In the intermetallic slab (Cs7[Sn9]2) compares the arrangement of pairs of symmetry‐related [Sn9]4– anions with the dimer ([Ge9]–[Ge9])6– in [K([2.2.2]crypt)]2Cs4([Ge9]–[Ge9]), in which the clusters are linked by a cluster‐exo bond. The shortest distance between atoms of such two clusters in 1 is 4.762 Å, e. g. there are no exo Sn‐Sn bonds. The [Sn9]4– anion has almost perfect C4v‐symmetry.  相似文献   

13.
Pyridinium Chlorometallates of Lanthanoid Elements. Crystal Structures of [HPy]2[LnCl5(Py)] mit Ln = Eu, Er, Yb und von [H(Py)2][YbCl4(Py)2] · Py The pyridinium chlorometallates [HPy]2[LnCl5(Py)] with Ln = Eu, Er and Yb, as well as [H(Py)2][YbCl4(Py)2]·Py have been obtained by the reaction of diacetone alcohol with solutions of the corresponding metal trichlorides in pyridine at 100 °C. According to the crystal structure determinations the anions [LnCl5(Py)]2— are linked by bifurcated Cl···H···Cl bridges with the protons of the [HPy]+ cations forming chains along [001]. The anions of [H(Py)2][YbCl4(Py)2]·Py form discrete octahedrons with trans‐positions of the pyridine ligands. [HPy]2[EuCl5(Py)] ( 1a ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1874.4(2), b = 1490.2(2), c = 741.5(1) pm, R1 = 0.0466. [HPy]2[ErCl5(Py)] ( 1b ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1864.3(1), b = 1480.7(2), c = 739.7(1) pm, R1 = 0.0314. [HPy]2[YbCl5(Py)] ( 1c ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1858.9(2), b = 1479.0(1), c = 736.8(1) pm, R1 = 0.0306. [H(Py)2][YbCl4(Py)2]·Py ( 2 ·Py): Space group Ia, Z = 4, lattice dimensions at —80 °C: a = 1865.5(1), b = 827.5(1), c = 1873.4(1) pm, ß = 103.97(1)°, R1 = 0.0258.  相似文献   

14.
New organotin(IV) carboxylates, [n-Bu2SnL2] (1), [Et2SnL2] (2), [Me2SnL2] (3), [n-Oct2SnL2] (4), [n-Bu3SnL] n (5), [Me3SnL] n (6), and [Ph3SnL] n (7), where L?=?3-(4-bromophenyl)-2-ethylacrylate, were synthesized and characterized by elemental analysis, FT-IR, and multinuclear NMR (1H, 13C, and 119Sn). Spectroscopic studies confirm coordination of L to the organotin moiety via COO group. Single-crystal X-ray analysis reveals bridging mode of coordination in 6. Packing diagram established a supramolecular cage-like structure for 6 due to Sn–O interactions (3.287?Å). Subsequent antimicrobial activities proved them to be active biologically.  相似文献   

15.
Although pure hydrogen cyanide can spontaneously polymerize or even explode, when initiated by small amounts of bases (e.g. CN?), the reaction of liquid HCN with [WCC]CN (WCC=weakly coordinating cation=Ph4P, Ph3PNPPh3=PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN)2]? and trihydrogen tetracyanide ions [CN(HCN)3]? from liquid HCN when a fast crystallization was carried out at low temperatures. X‐ray structure elucidation revealed hydrogen‐bridged linear [CN(HCN)2]? and Y‐shaped [CN(HCN)3]? molecular ions in the crystal. Both anions can be considered members of highly labile cyanide‐HCN solvates of the type [CN(HCN)n]? (n=1, 2, 3 …) as well as formal polypseudohalide ions.  相似文献   

16.
The synthesis and structures of the two CuI halide complexes [Cu5(dppm)(dppm?)2(OtBu)Cl2] and [Cu3(dppm)3Br2][CuBr2] (dppm = Ph2PCH2PPh2, dppm? = [Ph2PCHPPh2]?) are reported. The compounds were obtained by treating reaction mixtures of [CuOtBu] and dppm with dichloromethane or dibromomethane.  相似文献   

17.
By reacting [Pd( )(μ-Cl)]2 with AgClO4 in NCMe, the corresponding cationic complexes [Pd( )(NCMe)2]ClO4 ( = phenylazophenyl-C2,N1; dimethylbenzylamine-C2,N; 8-methylquinoline-C8,N) can be obtained. Solutions containing the cations [Pd( )(S)2]+ are obtained when the reaction is carried out in tetrahydrofuran or acetone (S). The treatment of these solutions with bidentate ligands (L—L) (Ph2PCH2PPh2,Ph2PNHPPh2 or Ph2PCH2PPh2CHC(O)Ph) gives the mononuclear [Pd( )(L3l)]ClO4 complexes, with L3l acting as a chelate ligand. On the other hand [Pd( (μ-Cl)]2 reacts with L3l (Ph2PCH2PPh2, Ph2PNHPPh2) yielding [Pd( )Cl(L3l)] with L3l acting as monodentate. The reactions between [Pd( )(NCMe)2]ClO4 and 2,2′-bipyrimidyl give rise to the formation of the mononuclear [Pd( ) (bipym)]ClO4 or binuclear [Pd2( )2(μ-bipym)](ClO4)2, [( )Pd(μ-bipym)Pd( )](ClO4)2 derivatives. Finally [Pd( )Cldppm] (dppm = Ph2PCH2PPh2) react with NaH producing the neutral complexes [Pd( )(ddppm)] (ddppm = Ph2PCHPPh2) which by reaction with HCl lead again to the starting materials [Pd( )Cl(dppm)].  相似文献   

18.
Combination of the [Ni(bpy)3]2+ cation complex and the [Pd(dmit)2] anion (dmit=C3S52−=1,3-dithiole-2thione-4,5-dithiolate) has resulted in the paramagnetic [Ni(bpy)3][Pd(dmit)2]·CH3CN compound, a suitable precursor for a molecular magnetic conductor. Its crystal structure consists of a Pd(dmit)2 anion arrangement that is quite different from segregated stack layers often found for M(dmit)2−based compounds. The reduction of the [Pd(dmit)2]- to the 2− charged anion in the title compound most probably is the result of a charge disproportionation between Pd(dmit)2 anions.  相似文献   

19.
The primary process in the reaction of hexaphenylditin with various substituted orthoquinones (Q) is shown to involve attack by the quinone at a phenyl ligand. The intermediate thus formed decomposes to yield Ph3Sn(SQ·), where S(Q·−) is the corresponding semiquinonate. Rearrangement of these species in solution gives rise to biradicals, while intramolecular electron transfer may lead to the formation and precipitation of Ph2Sn(CAT), where CAT2− is the corresponding substituted catecholate. The identification of these processes depends in part on electron paramagnetic resonance spectroscopy. The reaction of Ph3SnCl or Ph2SnCl2 with Na(TBSQ·) (TBSQ·−=3,5-di-tert-butyl-orthobenzosemiquinonate) results in the formation of Ph2Sn(TBSQ·), which can undergo redistribution and intramolecular electron transfer, so that the solution chemistry of these latter systems is similar to that of the products of the Sn2Ph6+Q reaction.  相似文献   

20.
《Polyhedron》1988,7(5):379-383
RhCl3·3H2O reacted with Na2dmit (dmit2−; 1,3-dithiole-2-thione-4,5-dithiolate anion) and [NBu4nOH in methanol to afford [NBu4n][Rh(dmit)2] (1) and [NBu4n]1.5[Rh(dmit)2] (2). Salt 1 was oxidized electrochemically in acetonitrile to afford [NBu4n]0.4[Rh(dmit)2] (3). Suspended powders of 1 or 2 reacted with iodine in hexane to afford [NBu4n][Rh(dmit)2][I3]1.3 (4) or [NBu4n]1.5[Rh(dmit)2[I3]0.4 (5). On the other hand, 1 dissolved in acetonitrile, reacted with bromine and iodine to yield [NBu4n]0.25[Rh(dmit)2Br] (6) and [NBu4n]0.35[Rh(dmit)2I] (7), respectively. All the salts behave as semi-conductors with electrical conductivities of 1 x (10−5 − 10−8) S cm−1 at 25°C measured for compacted pellets. Electronic absorption, ESR and X-ray photoelectron spectra of the salts are discussed.  相似文献   

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