(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇及其酯和卤代物的合成与表征

在氮气保护下,1-乙炔茚满醇与三苯基氢化锡进行游离基加成反应,获得加成物(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇(1);将加成物(1)与苯酐反应,得到新型邻苯二甲酸单酯有机锡衍生物(2);衍生物(2)分别与二丁基氧化锡和三苯基氧化锡进行脱水反应,分别获得两个新型邻苯二甲酸酯的有机锡衍生物(3)和(4).将加成物(1)与卤素反应后,与锡原子直接相连的苯基被取代,得到一卤代和二卤代物(5～10).通过元素分析、¹HNMR和IR等手段对化合物1～10进行了结构表征,确定了该类邻苯二甲酸单酯和邻苯二甲酸酯的有机锡衍生物的结构.并测定了加成物(1)和一溴代物(6)的晶体结构,在加成物(1)中,由于分子内存在较弱的O→Sn[0.2778(8)nm]配位作用,锡原子呈扭曲三角双锥构型.在一溴代物(6)分子中,存在分子内O→Sn[0.2364(2)nm]配位键,锡原子呈扭曲的三角双锥构型.该系列化合物分子内的O→Sn配位能力和Lewis酸性强弱的顺序为:二卤化物>一卤化物>加成物;氯代物>溴代物>碘代物>加成物.     

Synthesis, Characterization and Crystal Structure of （Z）-1-[2-（Triarylstannyl）vinyl]-1-indanols and Their Arylhalostannyl Derivatives

(Z)-1-[2-(Tri-o-tolylstannyl)vinyl]-1-indanol (1) and (Z)-1-[2-(tri-p-tolylstannyl)vinyl]-l-indanol (2) were synthesized by the addition reaction of 1-ethynylindanol with tri-o-tolyltin and tri-p-tolyltin hydride. The aryl groups in compound 1 and 2 were substituted by Br2 or I2 to yield monohalide derivatives (3-6). The compounds 1-6 were characterized by elemental analysis, ^1H NMR and FT-IR spectroscopy. The crystal structures of 1, 2 and 4 have been determined by single crystal X-ray diffraction analysis. The Sn atom in 1 and 2 exhibits a tetrahedral geometry distorted towards trigonal bipyramid due to a weak intramolecular interaction between Sn and the hydroxyl O atoms [0.2839(4) nm and 0.2744(5) nm], while the Sn atom in 4 adopts a trigonal bipyramidal geometry with a significant O→Sn(1) interaction [0.2552(5) nm].     

{4-t-Bu-2,6-[P(O)(O-i-Pr)2]2C6H2Sn}2: an intramolecularly coordinated organotin(I) compound with a Sn-Sn single bond, its disproportionation toward a diorganostannylene and elemental tin, and its oxidation with PhI(OAc)2

Syntheses of the intramolecularly coordinated organotin(I) compound {4-t-Bu-2,6-[P(O)(O-i-Pr)(2)](2)C(6)H(2)Sn}(2) (2), which crystallized in two different pseudopolymorphs 2 and 2·C(7)H(8), of the diorganostannylene {4-t-Bu-2,6-[P(O)(O-i-Pr)(2)](2)C(6)H(2)}(2)Sn (3) and of the organotin(II) acetate 4-t-Bu-2,6-[P(O)(O-i-Pr)(2)](2)C(6)H(2)SnOAc (4) are reported. The compounds were characterized by multinuclear NMR, IR (3 and 4), UV-vis spectroscopy (2), electrospray ionization mass spectrometry (3 and 4), and single-crystal X-ray diffraction analyses. Density functional theory calculations on compound 2 revealed the stabilizing effect of the intramolecular P═O → Sn coordination.     

Reactions of exo-substituted RSn9(3-) clusters with Pd: endohedral cluster formation and oxidative insertion

Pyridine/ethylenediamine solutions of [Sn(9)SnCy(3)](3-) (1) react with [Pd(PPh(3))(4)] to give new clusters [Pd@Sn(9)SnCy(3)](3-) (2) and [Pd@Sn(9)PdSnCy(3)](3-) (3), depending on stoichiometry. These compounds are formed sequentially and are the first transition metal derivates of exo-substituted Zintl clusters. Oxidative insertion of a Pd atom into the Pd@Sn(9)-SnCy(3) bond of 2 to form 3 represents a new reaction type for Zintl cluster compounds. The conversion Sn(9)(4-)→1→2→3 is a rare case in which charge and mass are conserved in a series of Zintl clusters. Complexes 1, 2, and 3 are all highly fluxional in solution. In all three clusters, the nine Sn vertices are in rapid exchange on the NMR timescale. In 1 and 2, the exo-SnCy(3) substituent also scrambles intramolecularly around the outside of the clusters. In 3, the SnCy(3) group remains attached to the vertex Pd atom. The disparate reactions with the other RSn(9)(3-) ions are discussed.     

The Neat Ternary Solid K(5-x) Co(1-x) Sn(9) with Endohedral [Co@Sn(9) ](5-) Cluster Units: A Precursor for Soluble Intermetalloid [Co(2) @Sn(17) ](5-) Clusters

A new type of Zintl phase is presented that contains endohedrally filled clusters and that allows for the formation of intermetalloid clusters in solution by a one-step synthesis. The intermetallic compound K(5-x) Co(1-x) Sn(9) was obtained by the reaction of a preformed Co?Sn alloy with potassium and tin at high temperatures. The diamagnetic saltlike ternary phase contains discrete [Co@Sn(9) ](5-) clusters that are separated by K(+) ions. The intermetallic compound K(5-x) Co(1-x) Sn(9) readily and incongruently dissolves in ethylenediamine and in the presence of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (2.2.2-crypt), thereby leading to the formation of crystalline [K([2.2.2]crypt)](5) [Co(2) Sn(17) ]. The novel polyanion [Co(2) Sn(17) ](5-) contains two Co-filled Sn(9) clusters that share one vertex. Both compounds were characterized by single-crystal X-ray structure analysis. The diamagnetism of K(5-x) Co(1-x) Sn(9) and the paramagnetism of [K([2.2.2]crypt)](5) [Co(2) Sn(17) ] have been confirmed by superconducting quantum interference device (SQUID) and EPR measurements, respectively. Quantum chemical calculations reveal an endohedral Co(1-) atom in an [Sn(9) ](4-) nido cluster for [Co@Sn(9) ](5-) and confirm the stability of the paramagnetic [Co(2) Sn(17) ](5-) unit.     

(Z)-1-三苯基锡基-3-对氯苯基-1-丁烯-3-醇及其卤代物的合成、表征和晶体结构

在氮气保护下,3-对氯苯基-1-丁炔-3-醇与三苯基氢化锡进行游离基加成反应,获得加成物(Z)-1-三苯基锡基-3-对氯苯基-1-丁烯-3-醇(1).加成物(1)与卤素反应后,与锡原子相连的苯基被取代,得到一卤代、二卤代和混合二卤代物(2-8).通过元素分析、¹HNMR和IR表征了化合物1～8的结构,并测定了加成物(1)、一溴代物(3)和二溴代物(5)的晶体结构.在加成物(1)的晶体结构中存在一对对映体,由于分子内存在较弱的O→Sn配位作用,构成以锡原子为中心的扭曲四面体构型.在化合物3和5分子中,存在分子内O→Sn配位键,构成以锡为中心的扭曲三角双锥构型.该系列化合物分子内的O→Sn配位能力和Lewis酸性强弱的顺序为:二卤化物>一卤化物>加成物;氯代物>溴代物>碘代物.     

Synthesis and structures of beta-diketiminatotin(II) halides, an amide and of Sn(=E)[{N(R)C(Ph)}2CH](NR2) (E = S or Se, R = SiMe3)

Treatment of [Li(L1)]2 (1) or K(L2) (2) with SnX2 in Et2O yielded the heteroleptic beta-diketiminatotin(II) halides Sn(L1)Cl (3a), Sn(L1)Br (3b) or Sn(L2)Cl (4), even when an excess of the alkali metal beta-diketiminate was used [L1={N(R)C(Ph)}2CH, L2={N(R)C(Ph)CHC(But)N(R)}, R = SiMe3]. From and half an equivalent each of SnCl2.2H2O and SnCl2, or one equivalent of SnCl2.2H2O, the product was Sn(L3)Cl (5) or Sn(L4)Cl (6), in which one or both of the N-R bonds of L1 had been hydrolytically cleaved; the compound Sn(L5)Cl (7) was similarly obtained from and an equivalent portion of SnCl2.2H2O [L3={N(R)C(Ph)CHC(But)N(H)}, L4={N(H)C(Ph)CHC(But)N(H)} and L5={N(H)C(Ph)}2CH]. The halide exchange between 3a and 3b, studied by two-dimensional (119)Sn{1H}-NMR spectroscopy, is attributed to implicate a (mu-Cl)(mu-Br)-dimeric intermediate or transition state. The 13C{1H}-NMR spectra of or showed two distinct resonances for each group, which coalesced on heating, corresponding to DeltaG(338 K)= 69.4 (3a) or 72.8 (3b) kJ mol(-1). The chloride ligand of was readily displaced by treatment with NaNR2, CF3SO3H or CH2(COPh)2, yielding Sn(L1)X [X = NR2 (8), O3SCF3 (9) or {OC(Ph)}2CH (10)]. Oxidative addition of sulfur or selenium to gave the tin(IV) terminal chalcogenides Sn(E)(L1)(NR2)[E = S (11) or Se (12)]. The X-ray structures of the cocrystal of 3a/3b and of the crystalline compounds 5, 6, 8, 11 and are presented, as well as multinuclear NMR spectra of each of the new compounds.     

Syntheses, molecular structures, electrochemical behavior, theoretical study, and antitumor activities of organotin(IV) complexes containing 1-(4-chlorophenyl)-1-cyclopentanecarboxylato ligands

The organotin(IV) compounds [Me(2)Sn(L)(2)] (1), [Et(2)Sn(L)(2)] (2), [(n)Bu(2)Sn(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph(2)Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin(IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn(6)O(6) core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.     

Reactivity of chalcogenostannate compounds: syntheses,crystal structures,and electronic properties of novel compounds containing discrete ternary anions [MII4(mu4-Se)(SnSe4)4]10- (MII = Zn,Mn)

Reactions of K4[SnSe4].1.5MeOH with ZnCl2 or MnCl2.4H2O in water/methanol mixtures yield novel compounds [K10(H2O)16(MeOH)0.5][M4(mu4-Se)(SnSe4)4] (M = Zn, 2; Mn, 3) in high yields; 2 and 3 contain the first discrete ternary Zn/Sn/Se or Mn/Sn/Se cluster anions. Both compounds were unambiguously characterized by X-ray diffraction (tetragonal, space groups P43212 and P41212, respectively) revealing chiral anionic structures within chiral crystals. Optical spectra of 2 and 3 indicate energy differences for the lowest electronic excitations (Eg = 2.57 eV, 2; 2.27 eV, 3) that are very close to the band gap values observed for mesoporous solids with polymeric M/Sn/E networks. DFT investigations on the electronic situation and first ESR studies agree in that they demonstrate a high-spin ground state in the case of 3 with 20 unpaired electrons at four uncoupled MnII centers.     

Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols

Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.     

In search of cyclohexane-like Sn6(12-): synthesis of Li2Ln5Sn7 (Ln = Ce, Pr, Sm, Eu) with an open-chain heptane-like Sn7(16-) instead

The title compounds were prepared by direct reactions of the corresponding elements at high temperature. They are isostructural and crystallize in the chiral orthorhombic space group P212121 (Li2Ce5Sn7: a = 6.273(1), b = 13.839(2), and c = 17.467(2) A; Li2Pr5Sn7: a = 6.241(1), b = 13.762(2), and c = 17.367(1) A; Li2Sm5Sn7: a = 6.262 (1), b = 13.809(1), and c = 17.432(1) A; Li2Eu5Sn7: a = 6.165(1), b = 13.562(2), and c = 17.128(1) A). The structure contains isolated Sn7 oligomers that resemble the carbon core of an open-chain heptane molecule C7H16. Although these heptamers are stacked along the a axis at a distance that is comparable to the distances within the heptamer, electronic structure calculations show that this intermolecular contact is nonbonding for a formal charge of 16- or higher per heptamer. A hypothetical lower charge of 14-, on the other hand, leads to positive and substantial bond-overlap population that would result in branched infinite chains of infinity[Sn714-]. Magnetic measurements of the Ce and Pr compounds indicate a 3+ oxidation state for the rare-earth cations and, therefore, 17 available electrons from the cations per formula unit. According to four-probe conductivity measurements, the compounds are metallic.     

Tin-based organo-Zintl ions: alkylation and alkenylation of Sn9(4-)

Reactions of nine-atom deltahedral clusters (Zintl ions) of tin, Sn 9 (4-), with alkyl chlorides, RCl (R = (t) Bu, (n) Bu, (s) Bu), and alkynes (Me3Si-C[triple bond]C-SiMe3, Ph-C[triple bond]CH) yielded the corresponding alkylated and alkenylated clusters [Sn 9-R] (3-). The triple bonds of the alkynes are hydrogenated to double bonds in the process. These are the first tin-based organo-Zintl ions, that is Zintl ions of tin that were subsequently functionalized with organic groups. They are analogous to the recently reported germanium-based derivatives. The (t) Bu-, vinyl-, and styrene-functionalized clusters [Sn 9- (t) Bu] (3-), [Sn 9-CH=CH 2] (3-), and [Sn 9-CH=CH-Ph] (3-), respectively, were structurally characterized in the solid state with [K(2,2,2-crypt)] (+) countercations and in solution by electrospray mass spectrometry. Crystal data: [K(2,2,2-crypt)] 3[Sn 9- (t) Bu].2py, triclinic, P1, a = 14.4259(3), b = 16.2725(4), and c = 22.5593(5) A, alpha = 86.092(1), beta = 78.952(1), and gamma = 65.114(1) degrees , V = 4714.48(7) A (3), Z = 2; [K(2,2,2-crypt)] 3[Sn 9-CH=CH 2].2py, triclinic, P-1, a = 15.6988(3), b = 17.4195(4), and c = 17.4432(4) A, alpha = 86.299(1), beta = 81.566(1), and gamma = 85.349(1) degrees , V = 4696.27(18) A (3), Z = 2; [K(2,2,2-crypt)] 3[Sn 9-CH=CH-Ph].tol.0.75py, monoclinic, C2/c, a = 38.5883(9), b = 23.3893(5), and c = 25.0192(5) A, beta = 120.269(1) degrees , V = 19502.6(7) A (3), Z = 8.     

Intramolecular interactions in μ‐oxido‐bis{bis[2‐(dimethylaminomethyl)phenyl]stannol}

The title compound, [Sn₂(C₉H₁₂N)₄O(OH)₂], consists of two [2‐(Me₂NCH₂)C₆H₄]₂SnOH units bridged by an O atom located on a twofold rotation axis. The unique Sn atom is six‐coordinated with a (C,N)₂SnO₂ octahedral core, as a result of the strong intramolecular N→Sn dative coordination trans to the Sn—O bonds [N—Sn—O = 170.24 (12) and 167.83 (10)°]. Owing to the presence of intermolecular H...phenyl contacts, the molecules are arranged in a ladder‐like structure.     

cyclo-CH2[Sn(CI2)CH2Si(Me2)]2O]: synthesis and complexation behaviour of a novel, cyclic, bidentate Lewis acid and its conversion into a tin-containing fluorosilane with intermolecular Si-F...Sn bridges

Acid-catalysed hydrolysis of [CH2[(Sn(Ph2)CH2Si(OiPr)Me2]2] followed by subsequent reaction with mercuric chloride in acetone afforded the novel silicon- and tin-containing eight-membered ring [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] in good yield, the crystal structure of which is reported. 119Sn NMR and X-ray studies indicate that [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] acts as a bidentate Lewis acid towards chloride ions exclusively forming the 1:1 complex [(Ph3P)2N]+[cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2OCl]- upon addition of [(Ph3P)2N]+Cl- . Also reported are the synthesis and structure of [K(dibenzo[18]crown-6)]+[cyclo-CH2(Sn(Cl2)CH2Si(Me2)]2OF]-, the first completely characterised organostannate with a C2SnCl2F- substituent pattern. No ring-opening polymerisation could be achieved for [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] or for its perphenylated derivative [cyclo-CH2[Sn(Ph2)CH2Si(Me2)]2O]. The reaction of [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] with Me3O+BF4- gave the tin-containing fluorosilane [CH2[Sn(Cl2)CH2Si(F)Me2]2], in which the Si-F bond is activated by intermolecular Si-F...Sn interactions in the solid state.     

Unusual syntheses, structures, and electronic properties of compounds containing ternary, T3-type supertetrahedral M/Sn/S anions [M5Sn(mu3-S)4(SnS4)4](10- (M = Zn, Co)

A recently discovered series of quaternary compounds of the general type [K(m)(ROH)(n)()][M(x)Sn(y)()Se(z)] (R = H, Me), containing ternary anions with [SnSe(4)](4-)-coordinated transition metal centers (M = Co, Mn, Zn, Cd, Hg) has now been extended by the synthesis and characterization of the two ortho-thiostannate-coordinated species, [Na(10)(H(2)O)(32)][M(5)Sn(mu(3)-S)(4)(SnS(4))(4)].2H(2)O (M = Zn (1), Co (2)). The central structural motifs of compounds 1 and 2 are highly charged [M(5)Sn(mu(3)-S)(4)(SnS(4))(4)](10-) anions, being the first T3-type supertetrahedral ternary anions reported to date. The exposure of single crystals of 2 to a dynamic vacuum for several hours resulted in the reversible formation of a partially dehydrated, but still monocrystalline material of the composition [Na(10)(H(2)O)(6)][Co(5)Sn(mu(3)-S)(4)(SnS(4))(4)] (3). The loss of 28 of the 34 water molecules only slightly affects the internal structure of the ternary anion in 3 and leads to a significant compacting of the crystal structure with closer linkage of the [Co(5)Sn(5)S(20)](10-) cluster units via the Na(+) cations. Magnetic measurements on 3 show that the ground state of the Co/Sn/S cluster is S = 1/2, indicating a significant antiferromagnetic coupling between the Co centers, which has also been rationalized by DFT investigations of the electronic situation in the ternary subunits of 1-3.     

Intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)2]2C6H2Sn(X)W(CO)5 (X = Cl, F, PPh2, PPh2[W(CO)5]). Syntheses and reactivity

The synthesis of the intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)Sn(X)W(CO)(5) (1, X = Cl; 2, X = F; 3, X = PPh(2)) and of 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)Sn[W(CO)(5)]PPh(2)[W(CO)(5)], 4, are reported. UV-irradiation of compound 4 in tetrahydrofurane serendipitously gave the bis(organostannylene) tungsten tetracarbonyl complex cyclo-O(2)W[OSn(R)](2)W(CO)(4) (R = 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)), 5, that contains an unprecedented W(0)-Sn-O-W(vi) bond sequence. The compounds 1-5 were characterized by means of single crystal X-ray diffraction analysis, (1)H, (13)C, (19)F, (31)P, (119)Sn NMR, and IR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and elemental analysis. Compound 4 features a hindered rotation about the Sn-P bond.     

Synthesis and spectroscopic and X-ray structural characterization of R2Sn(IV)-oxydiacetate and -iminodiacetate complexes

Seven novel R2Sn(IV)-oxydiacetate (oda) and -iminodiacetate (ida) compounds of the form [R2Sn(oda)(H2O)]2 (R = Me, nBu, and Ph) (1-3), [(R2SnCl)2(oda)(H2O)2]n (R = Et, iBu, and tBu) (4-6), and [Me2Sn(ida)(MeOH)]2 (7) have been synthesized and characterized by IR, 1H, 13C, and 119Sn NMR (solution), solid-state 119Sn CPMAS NMR, and (119m)Sn M?ssbauer spectroscopy. The crystal structure of [Me2Sn(oda)(H2O)]2, 1, shows it to be dinuclear (centrosymmetric), with two seven-coordinated tin atoms, bridged by one arm of the carboxylate group from each oda. By contrast, the crystal structure of [(Et2SnCl)2(oda)(H2O)2]n, 4, comprises a zigzag polymeric assembly containing a pair of different alternating subunits, {Et2SnCl(H2O)} and {Et2SnCl(H2O)(oda)}, which are connected by way of bridging oda carboxylates, thus giving seven-coordinate tin centers in both components. Finally, the structure of [Me2Sn(ida)(MeOH)]2, 7, also centrosymmetric dinuclear, is comprised of a pair of mononuclear units with seven-coordinate tin. The 119Sn solid-state CPMAS NMR and (119m)Sn Mossbauer suggest the presence of seven-coordinate Sn metal atoms in some derivatives and the existence of two different tin sites in the [(R2SnCl)2(oda)(H2O)2]n compounds.     

Cluster oxalate complexes [M3(mu3-Q)(mu2-Q2)3(C2O4)3]2- and [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2- (M = Mo, W; Q = S, Se): mechanochemical synthesis and crystal structure

Mechanochemical reaction of cluster coordination polymers 1infinity[M3Q7Br4] (M = Mo, W; Q = S, Se) with solid K2C2O4 leads to cluster core excision with the formation of anionic complexes [M3Q7(C2O4)3]2-. Extraction of the reaction mixture with water followed by crystallization gives crystalline K2[M3Q7(C2O4)3].0.5KBr.nH2O (M = Mo, Q = S, n = 3 (1); M = Mo, Q = Se, n = 4 (2); M = W, Q = S, n = 5 (3)). Cs2[Mo3S7(C2O4)3].0.5CsCl.3.5H2O (4) and (Et4N)1.5H0.5K{[Mo3S7(C2O4)3]Br}.2H2O (5) were also prepared. Close Q...Br contacts result in the formation of ionic triples {[M3Q7(C2O4)3](2)Br}5- in 1-4 and the 1:1 adduct {[Mo3S7(C2O4)3]Br}3- in 5. Treatment of 1 or 2 with PPh(3) leads to chalcogen abstraction with the formation of [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2-, isolated as (Ph4P)2[Mo3(mu3-S)(mu2-S)3(C2O4)3(H2O)3].11H2O (6) and (Ph4P2[Mo3(mu3-Se)(mu2-Se)3(C2O4)3(H2O)3].8.5H2O.0.5C2H5OH (7). All compounds were characterized by X-ray structure analysis. IR, Raman, electronic, and 77Se NMR spectra are also reported. Thermal decomposition of 1-3 was studied by thermogravimetry.     

Synthesis,halogenation and structural characterization of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cyclododecanol

Synthesis and characterisation of (Z)-1-[2(triphenylstannyl)vinyl]-l-cyclododecanol, c-(CH₂)₁₁C(OH)CH=CHSnPh₃, are reported, together with its halogenation by I₂, Br₂ and ICI to yield derivatives of the types c-(CH₂)₁₁C(OH)CH=CHSnPhs_?nX_n (n=1, 2; X=I, Br, Cl, respectively). The molecular structures of two compounds have been determined by X-ray diffraction analysis. The tin atom exhibits a distorted tetrahedral geometry in the crystal of (Z)-l-[2–(triphenylstannyI)vinyl]-l-cyclododecanol, but a trigonal bipyramidal geometry in the monoiodo-derivative (Z)-l-[2]-(diphenyliodo-stannyl)vinyl)-1-cyclododecanol and other derivatives, in which significant intramolecular coordinative interaction HO→Sn ia observed. And the formation of a five-membered tin containing ring is significant for their antitumour activities.     

Synthesis and Structure of a Mixed Phosphine-Thiolato Polymer with a Linear Chain Network [Ag2 (μ2-dppe)3 (S-mbo)2]n · 2nDMF [dppe = 1,2-Bis (diphenylphosphino)ethane, mbo= 2-Mercaptobenzoxazole]

Diphosphino organochalcogenide metal complexes have been investigated presently fortheir possible use as anti-cancer agents[1-3]. However, the area of silver complexes withmixed phosphine-thiolato ligands has scarcely been touched[4]. As a heterocyclic thiolato lig-and with potential S and N donors, 2-mercaptobenzoxazole (Hmbo) is interesting because ofthe structural chemistry of its multifunctional coordination modes (unidentate-N, unidentate-S or bidentate-N : S)[5-8]. Until now, Ag-mbo complex has been unknown to our knowl-edge, despite the fact that its complexes of Sn[5] , Au[6] and Li[7,8] have been reported. Hereinwe report the X-ray crystal structure of a self-assembled coordination polymer[Ag2(μ2-dppe)3(S-mbo)2]n · 2nDMF(dppe=1,2-bis(diphenylphosphino)ethane, Hmbo=2-mercaptobenzoxazole, DMF = dimethyl formamide).