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1.
The compound [Os3(CO)10(μ-Cl)(μ-AuPPh3)] (2) was prepared from the reaction between [Os3(CO)10(NCMe)2] (1) and [AuClPPh3] under mild conditions. The reaction of 2 with 4-mercaptopyridine (4-pyS) ligand yielded compounds [Os3(CO)10(μ-H)(μ-SC5H4N)] (4), formed by isolobal replacement of the fragment [AuPPh3]+ by H+ and [Os3(CO)10(μ-AuPPh3)(μ-SC5H4N)] (5). [Os3(CO)10(μ-H)(μ-SC5H4N)] (4) was also obtained by substitution of two acetonitrile ligands in the activated cluster 1 by 4-pyS, at room temperature in dichloromethane. Compounds 2-5 were characterized spectroscopically and the molecular structures of 4 and 5 in the solid state were obtained by single crystal X-ray diffraction studies.  相似文献   

2.
RSeCCPh (1a, R = Et; 1b, R = n-Bu; 1c, R = Ph; 1d, R = 2,4,6-Me3C6H2) reacts with equimolar amounts of Fe2(CO)9 (2) to give [(μ-SeR)(μ-σ,π-CCPh)]Fe2(CO)6 (3a, R = Et; 3b, R = n-Bu; 3c, R = Ph; 3d, R = 2,4,6-Me3C6H2).Complexes 3a-3d exist as two isomers, depending on the axial or equatorial position of R at selenium.Addition of P(OiC3H7)3 (4) to 3d affords {(μ-Se-2,4,6-Me3C6H2)[μ-η1-CCPh(P(OiC3H7)3)]}Fe2(CO)6 (5) along with {(μ-Se-2,4,6-Me3C6H2)[μ-η11-PhCC(P(OiC3H7)3)]}Fe2(CO)6 (6).The solid-state structures of 3d, 5 and 6 were determined by single X-ray structure analysis.In mononuclear 3d the Fe(CO)3 fragments are bridged by a μ-Se-2,4,6-Me3C6H2 and a μ-σ,π-CCPh unit, resulting in an over-all butterfly arrangement.Due to steric reasons, the mesityl group is pointing away from the PhCC entity and hence, is located in an equatorial position.Compounds 5 and 6, which co-crystallise in the ratio of 7:93, feature aμ-bridging 2,4,6-Me3C6H2Se unit and either a vinylidenic CCPh(P(OiC3H7)3) (complex 5) or a olefinic PhCC(P(OiC3H7)3) (complex 6) building block of which the latter entity is part of a diiron cyclobutene ring.  相似文献   

3.
The synthesis and spectroscopic properties of a Na complex with ligand 3-aminopyrazine-2-carboxylic acid were described. The resulting complex was characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy and single crystal X-ray diffraction method. The title compound crystallizes in the triclinic system with space group . The crystalline structure of this compound consists of supramolecular architectures involving strong intramolecular N—H…O in pyrazine molecules and intermolecular O—H…N, O—H…O, and N—H…N hydrogen bonds between substituted pyrazine and water molecules.  相似文献   

4.
5.

Abstract  

Thermolysis of cis-Fe(CO)4(SiCl3)2 results in the formation of the novel compound Fe2(CO)62-SiCl2)3, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe2(CO)6(SiCl2)3, including CO dissociation and chlorine abstraction by a SiCl3 radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.  相似文献   

6.
Photolysis of a hexane solution containing Fe(CO)5 and CS2 leads to desulfurization and formation of a novel cluster [{Fe2(CO)6}2(μ-C2S3)] (1). Its molecular structure was determined by single crystal X-ray diffraction methods and shown to consist of two distinct Fe2(CO)6 units linked by an unusual C2S3 unit.  相似文献   

7.
四核铁配合物[Fe4(NTB)42-O)24-Suc)](ClO4)6与DNA具有较强的结合作用,结合常数kb达(5.9±0.4)×105 L·mol-1。该多核铁配合物由水解途径促进DNA断裂,在酸性及低离子浓度条件下的促进作用较为显著。动力学分析表明DNA水解没有明显的序列选择性,质粒DNA从超螺旋转变为切口形式符合饱和酶动力学规律,饱和速率常数ksat=0.014 min-1。  相似文献   

8.
The title dimanganese complexes react with NO (5% in N2) at room temperature to give as major products the corresponding hexanitrosyl derivatives [Mn2(NO)6(μ-L2)] in moderate yields, and they react rapidly with NO2 to give the corresponding hydride derivatives [Mn2(μ-H)(μ-NO2)(CO)6(μ-L2)], these having a nitrite ligand bridging the dimetal centre through the N and O atoms. The dppm-bridged dihydride also reacts selectively at 273 K with (PPN)NO2 to give first the nitro derivative (PPN)[Mn2(μ-H)(H)(NO2)(CO)6(μ-dppm)], which then transforms into the nitrosyl complex (PPN)[Mn2(μ-CO)(CO)5(NO)(μ-dppm)] at room temperature or above (dppm = Ph2PCH2PPh2; PPN+ = [N(PPh3)2]+). The latter anion reacts with (NH4)PF6 to give the hydride-bridged nitrosyl complex [Mn2(μ-H)(μ-NO)(CO)6(μ-dppm)] and with [AuCl(PPh3)] to give the trinuclear cluster [AuMn2(μ-NO)(CO)6(μ-dppm)(PPh3)] (Mn-Au = ca. 2.68 Å; Mn-Mn = 2.879(2) Å). Both products are derived from the addition of the added electrophile at the intermetallic bond and rearrangement of the nitrosyl ligand into a bridging position. In contrast, methylation of the anion with CF3SO3Me takes place at the nitrosyl ligand to yield the unstable methoxylimide derivative [Mn2(μ-NOMe)(CO)6(μ-dppm)]. Analogous reactions at the nitrosyl ligand take place upon the addition of HBF4·OEt2 to the nitrosyl-bridged hydrides [Mn2(μ-H)(μ-NO)(CO)n(μ-dppm)m] (n = 6, m = 1; n = 4, m = 2) to give the corresponding hydroxylimide derivatives [Mn2(μ-H)(μ-NOH)(CO)n(μ-dppm)m]BF4, which were also thermally unstable and could not be isolated nor fully characterized.  相似文献   

9.
Two novel polynuclear complexes with methanoate anions and 3-hydroxypyridine ligands [Cu(μ-HCO2)2(3-pyOH)]n (1) and [Cu2(μ-HCO2)2(μ-3-pyOH)2(3-pyOH)2(HCO2)2]n (2), respectively, were synthesized and characterized. The central copper atom in 1 is surrounded by four methanoates and a 3-pyOH molecule, forming a square-pyramidal CuO3NO chromophore. All the methanoates are bidentate and serve as bridges between the adjacent copper ions via syn-anti and anti–anti coordination. The basal square coordination axes are formed by O(syn), N(3-pyOH) (1.974(2), 2.016(2) Å) and O(anti), O(anti) (1.945(2), 1.960(2) Å), while the third O(anti) (2.247(2) Å) is on the top of the pyramid. A ferromagnetic transition with an exchange constant 2J/kB = 9.2 cm−1 is found for 1 below 20 K. This interaction probably takes place through two syn-anti methanoates extended in a chain through the 2D structure. On the other hand, two monoatomic Cu–O–Cu intra-dinuclear asymmetric (1.986(2), 2.415(2) Å) bridges of two methanoates in [Cu2(HCO2)4(3-pyOH)4] (2) are present. An elongated distorted octahedral coordination sphere around each copper(II) atom is completed by an additional monodentate terminal methanoate (1.975(2) Å), two N-coordinated 3-pyOH (2.005(2), 2.002(2) Å) and the third weakly O-coordinated 3-pyOH (2.732(2) Å). Although a shorter Cu?Cu distance is noticed in 2 than in 1 (4.690(1) Å 1, 3.442(1) Å 2), much weaker ferromagnetism is found in 2.  相似文献   

10.
Relativistic scalar and spin-orbit density functional calculations of the electronic structure, Nucleus-Independent Chemical Shift (NICS) index and ELF function of the [Re2(CO)8(μ-BiPh)2] and [Re2(CO)8(μ-BiPh2)2] clusters are reported. We show here that the [Re2(CO)8(μ-BiPh)2] cluster has large negative NICS values in the region defined by the Re-Bi-Re-Bi four-membered ring and the ELF function shows significant electron delocalization density in the center of the metallic ring, thus indicating an aromatic cluster. In contrast the Re-Bi-Re-Bi four-membered ring in the [Re2(CO)8(μ-BiPh2)2] cluster has negligible paratropic ring currents and the ELF function shows a low-density region within the metallic ring indicating that aromaticity is switched off. However, the phenyl ligands in both clusters show the expected aromatic character.  相似文献   

11.
Treatment of unsaturated [Os3(CO)83-Ph2PCH2P(Ph)C6H4}(μ-H)] (2) with tBuNC at room temperature gives [Os3(CO)8(CNBut)){μ3-Ph2PCH2P(Ph)C6H4}(μ-H)] (3) which on thermolysis in refluxing toluene furnishes [Os3(CO)7(CNBut){μ3-Ph2PCHP(Ph)C6H4}(μ-H)2] (4). Reaction of the labile complex [Os3(CO)9(μ-dppm)(NCMe)] (5) with tBuNC at room temperature affords the substitution product [Os3(CO)9(μ-dppm)(CNBut)] (6). Thermolysis of 6 in refluxing toluene gives 4. On the other hand, the reaction of unsaturated [Os3(CO)932-C7H3(2-Me)NS}(μ-H)] (7) with tBuNC yields the addition product [Os3(CO)9(CNBut){μ-η2-C7H3(2-Me)NS}(μ-H)] (8) which on decarbonylation in refluxing toluene gives unsaturated [Os3(CO)8(CNBut){μ32-C7H3(2-Me)NS}(μ-H)] (9). Compound 9 reacts with PPh3 at room temperature to give the adduct [Os3(CO)8(PPh3)(CNBut){μ-η2-C7H3(2-Me)NS(μ-H)] (10). Compound 8 exists as two isomers in solution whereas 10 occurs in four isomeric forms. The molecular structures of 3, 6, 8, and 10 have been determined by X-ray diffraction studies.  相似文献   

12.
The reaction between [Ru3(CO)10(NCMe)2] and [AuClPPh3] gave compound [Ru3(CO)10(μ-Cl)(μ-AuPPh3)] (1) in quantitative yield under very mild conditions. The reaction of 1 with 4-mercaptopyridine (4-pyS) using ultrasonic reaction conditions gave the heteronuclear compound [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] (2) in moderate yield. There was no spectroscopic evidence that indicates the formation of the hydride isolobal analog in this reaction. The homonuclear cluster [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)] (3) was prepared by a selective reaction employing the ruthenium-diphosphine derivative [Ru3(CO)10(μ-dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) with 4-pyS in THF solution. The isolobal analog to compound 3, compound [Ru3(CO)8(μ-AuPPh3)(μ-SC5H4N)(μ-dppe)] (4) was synthesized by the reaction between compound 2 and dppe in refluxing dichloromethane. Compounds 1-4 were characterized in solution by spectroscopic methods and the molecular structure of compounds 2 and 3 in the solid state was obtained by single crystal X-ray diffraction studies.  相似文献   

13.
A convenient synthesis and the characterization of six new electronically and coordinatively unsaturated complexes of the formula [Ru2(CO)4(μ-H)(μ-PtBu2)(μ-L2)] (2b-g) (RuRu) is described exhibiting a close relation to the known [Ru2(CO)4(μ-H)(μ-PtBu2)(μ-dppm)] (2a). The complexes 2b-g were obtained in a kind of one-pot synthesis starting from [Ru3(CO)12] and PtBu2H in the first step followed by the reaction with the bidentate bridging ligand in the second step. The method was developed for the following bridging ligands (μ-L2): dmpm (2b, dmpm = Me2PCH2PMe2), dcypm (2c, dcypm = Cy2PCH2PCy2), dppen (2d, dppen = Ph2PC(=CH2)PPh2), dpppha (2e, dpppha = Ph2PN(Ph)PPh2), dpppra (2f, dpppra = Ph2PN(Pr)PPh2), and dppbza (2g, dppbza = Ph2PN(CH2Ph)PPh2). The molecular structures of all new complexes 2bg were determined by X-ray diffraction.  相似文献   

14.
Oxo/hydoxo zirconium(IV) complex of the general formula [Zr63-O)43-OH)4(OOCCH2tBu)92-OH)3]2 has been isolated, when Zr(OiPr)4 reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P63/m (no. 176)). Structure consists of dimers composed of [Zr63-O)43-OH)4(OOCCH2tBu)9] sub-units, linked by six μ2-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ2-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr63-O)43-OH)4(OOCCH2tBu)92-OH)3]2 proceeds with complete conversion to ZrO2 (monoclinic form) between 603 and 803 K.  相似文献   

15.
The γ-hydroxypropyl-functionalised diiron dithiolate complex [Fe2(CO)6(μ-SCH2CH2CH2OH)2] is prepared upon thermolysis of Fe3(CO)12 and HO(CH2)3SH and further reaction with dppm (dppm = Ph2PCH2PPh2) affords [Fe2(CO)4(μ-dppm)(μ-SCH2CH2CH2OH)2]. From the reaction of Fe3(CO)12 with dppm(S2) a minor product is the tetrairon cluster, [{Fe2(CO)6(μ-SCH2CH2CH2OH)}24-S)], the mode of formation of which is unclear. It has been crystallographically characterised and adopts a μ4-S bridged double butterfly structure which is compared with other crystallographically characterised complexes of this type. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

16.
Reactions of [(dtc)2Mo2(S)2(μ-S)2] with one or two equivalents of CuBr in CH2Cl2 afforded two new heterobimetallic sulfide clusters, [(dtc)2Mo23-S)(μ-S)3(CuBr)] (1) and [(dtc)2Mo23-S)4(CuBr)2] (2). Both compounds were characterized by elemental analysis, IR, UV-vis and X-ray analysis. Compound 1 contains a butterfly-shaped Mo2S4Cu core in which one CuBr unit is coordinated by one bridging S and two terminal S atoms of the [(dtc)2Mo2(S)2(μ-S)2] moiety. In the structure of 2, one [(dtc)2Mo2(S)2(μ-S)2] moiety and two CuBr units are held together by six Cu-μ3-S bonds, forming a cubane-like Mo2S4Cu2 core.  相似文献   

17.
Reaction of P2Ph4 with the diyne-diol complex [{Co2(CO)6}2(μ-η2:μ-η2-HOCH2CCCCCH2OH)] in toluene at 65 °C gives [{Co2(μ-P2Ph4)(CO)4}{Co2(CO)6}(μ-η2:μ-η2-HOCH2CCCCCH2OH)] (1). Thermolysis of 1 at 95 °C leads to [{Co2(CO)5}2(μ-P2Ph4)(μ-η2:μ-η2-HOCH2CCCCCH2OH)](2) and (μ2-PPh2)(μ2-CO)(CO)7] (3). The structures of 1-3 have been established by X-ray crystallography. In 1, a pseudoequatorial P2Ph4 ligand bridges the cobalt-cobalt bond of a Co2(CC)(CO)4 unit. By contrast, in isomeric 2, a pseudoaxial P2Ph4 ligand spans two Co2(CC)(CO)5 units, a new coordination mode for [{Co2(CO)5L}2(μ-η2:μ-η2-diyne)] complexes. Complex 3 arises from dehydration-cyclocarbonylation of the diyne-diol in 1 to give a 2(5H)-furanone, a process that has not been previously reported. Reaction of HOCH2CCCCCH2OH with [Co2(μ-PPh2)2(CO)6] at 80 °C in toluene gave [Co3(μ-PPh2)3(CO)6], [Co2(CO)6(μ-η2-HOCH2CCCCCH2OH)] and [Co2{μ-η4-PPh2C(CCCH2OH)C(CH2OH)CO}(μ-PPh2)(CO)4] (4). The regiochemistry of 4 was confirmed by X-ray crystallography.  相似文献   

18.
A new polymer azido-bridged copper(II) complex [Cu4(En)21,1-N3)41,1,1-N3)21,3-N3)2] n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu4(En)21,1-N3)41,1,1-N3)21,3-N3)2], in which the azido ions display three different bridging modes.  相似文献   

19.
Reaction of silver(I) halides with PPh3 in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag2X2(μ-S-pySH)2(PPh3)2] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag2S2 cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state 31P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.  相似文献   

20.
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (4) reacts with refluxing toluene to form the clusters Ru2Os3(μ-H)2(CO)16 (5) RuOs3(CO)9(μ-CO)26-C6H5Me) (6) and Ru2Os3(CO)12(μ-CO)(η6-C6H5Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated.  相似文献   

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