ucc第九期部11级BingjieXu级生KaiHou12

1、Syntheses,crystalstructures ofacomplexwithmercapto-thiadiazole ligand involving in situ ligand synthesisBingjieXu11级本科生) KaiHouMinQiao11级本科生）LinkeACo(ddc)3 (1), (Hddc = N,N-acid) has been sfully synthesized. Notably, situ ligand reaction he formation of 1, in which the ligand 4-Hptt reacted with DMF

2、 generate the ligand sible SchemeSyntheses,crystalstructures ofacomplexwithmercapto-thiadiazole ligand involving in situ ligand synthesisBingjieXu11级本科生) KaiHouMinQiao11级本科生）LinkeACo(ddc)3 (1), (Hddc = N,N-acid) has been sfully synthesized. Notably, situ ligand reaction he formation of 1, in which t

3、he ligand 4-Hptt reacted with DMF generate the ligand sible Scheme1.Ligends 4-HpttandHddchisof the formation The 4-Hptt was prepared according to the literature method 12. Other chemical, reagents, and solvents lly thiadiazole derivatives, sess a purchased from l and used variety of biological activ

4、ity, have been extensively researched in the elds of pesticides and medicines 1,2. However, these compounds with N/S-donor like mercapto- thiadiazole and its derivates are relatively few used as ligands in coordination chemistry 3. Therefore, it deserves further attention for the sake of more versat

5、ile structures and properties he future.On the other hand, anic ligands usually are synthesizedbytheconventionalmethods,butsomefurther purication. The fluorescence spectra for the sles were measured at room temperature on a 850 SynthesisofCo(ddc)3A mixture ofCoCl26H2O (7.1 mg, 0.03 mmol), 4-Hptt (11

6、.7 mg,0.06 mmol), H2O (5 mL) and DMF (1 mL) was sealedina 25mL Teflon-lined stainless steel autoclave and heated at 130 C for 4 days, and then slowly cooled to room temperature. Pale yellow crystals of complex 1 were separated suitably for X-ray diffraction (Yield: 40%).2.3 X-ray crystallographic de

7、terminations for the The data of complex 1 was collected by using a which are sible or not easily achieved via Until now, several types of in situ ligand reactions appeared under hydro(solvo)thermal conditions, include alkylation, hydroxylation, carboncarbon bond formation, hydrolysis, triazole and

8、tetrazole formation, etc 4,79.Theseinsituligandreactionshaveattractedmuch attention because they are effective ways to generateunexpected structures and riguing net- monochromatic Mo Ka radiation (k = 0.71073 ). Single crystals were selected and mounted on a glass fiber. topologies10,11.Toourbestkno

9、wledge,thestudyonsitu ligand transformationabout mercapto-thiadiazole and its derivates has not been reported. Therefore, we data were collected emperature of 291(3) K corrected for Lorentz- polarization effects. The structure was solvedby directmethodsandrefined wi full-matrix least-squares techniq

10、ue based on F2 with the SHELXL-97 crystallographic software package 13. All non-hydrogen atoms were refined anisotropically. The hydrogen taken sibility of in situ transformationaboutmercapto-thiadiazoleanditshisr,weused5-(4-pyridyl)-1,3,4-thiadiazole-thione (4-Hptt) (Scheme 1) as a ligand to assemb

11、le with metal ion. As a consequence, one mononuclear were assigned with factors and included geometrical mon isotropic displacement in the final refinement by Co(ddc)3(1)(Hddc wassynthesizedsfullyundersolvothermalinwhichtheHddcligandwasobtainedfromthereaction4-Hptt and DMF. The discussed in detail.s

12、ible reaction mechanism ResultsandsThe 4-Hptt (4-Hptt = 5-(4-pyridyl)-1,3,4-thiadiazole-14.Moreimportantly,ermolecularthione) was usedasthe anic ligand totheseoa3Darchitecture (shownin Fig.with metalionat 130 C for 4daysinH2O/DMFsolvent systems. Its worth t the ligand unexpectedly obtained incomplex

13、1, in which the The 4-Hptt (4-Hptt = 5-(4-pyridyl)-1,3,4-thiadiazole-14.Moreimportantly,ermolecularthione) was usedasthe anic ligand totheseoa3Darchitecture (shownin Fig.with metalionat 130 C for 4daysinH2O/DMFsolvent systems. Its worth t the ligand unexpectedly obtained incomplex1, in which the lig

14、and Hptt was o Hddc and transition metal was oxidized to Co(III) ion. The study t transition metal Co(II) plays a unique catalytic rolein situ transformation of 4-Hptt, then Co(II) is oxidized Co(III) he presence of the Hddc ligand, forming complex 1 14. siblyschematic mechanism forformationofHddcis

15、illustratedinSchemeFigure 1a.Coordination environment of the Co(III)center in complex1.Ellipsoids aredrawnatthe30%probabilitylevelwith all hydrogens omitted for clarity.Figure1b. The 3Dframeworkof 1viewedalongtheaIn summary, mon in situ ligand Schemesiblemechanismfortheformationof of mercapto-thiadi

16、azole derivate has been achieved hydrothermal he presence of Co(II) he formation of (1), which the in situ ligand synthesis of Hddc from Single-crystal X-ray ysis tmercapto-thiadiazole ringhasnotpreviouslybeen reported. But tuned by different metal salts, the in situ synthesis mononuclearcomplex1bel

17、ongstomonoclinicspaceP21/c. As shown Fig. 1a, the cobalt centre Hddc is not occurred. The result t metal coordinated by six sulphur atoms from ligands (Hddc) Co(II) plays great role in ligand transformation under hydrothermalconditions.Thecurrentresultswillencourage us to further work on this theme.

18、it isin distortedoctahedral geometry with S1and S4in the ition, while S2, S3, S5 and S6 atoms equatorial plane. The asymmetric unit of 1 contains Co(III) ion and three ligands Hddc. Each ligand adopts biden e mode to chelate the cobalt centre to form a fourThe authors nk the National Natural Science

19、 Foundation (Nos. 20801048, 20971110 and J1210060), Program for New Century Excellent Talents of Ministry of Education of China (NCET-07-0765), and the ring which is the same t (CH2 15. The CoS lengths ranging from 2.2531(12) to 2.2734(13) for chelate rings are t sFoundationofHenan(ecpzdtc = 1-ethox

20、ycarbonyl-piperazine-carbodithioate) (2.2645(15)2.2766(15) ) 14. The S CoS bond angles in which S atoms come from a Y.Luo,S.Zhang,Z.J.Liu,W.Chen,J.Fu,Q.F.Zeng,H.L. Zhu, Eur. J. Med. Chem. 2013, 64 , 54.Y.C. Pan, Y. Wen, X.Y. Guo, P. Song, S. Shen, Y.P. Hddcherangof76.24(4)Lto76.61(4)L.Thesulfur bond

21、 lengths of the chelate rings are C3S1 = 1.712(4), C3S2 = 1.704(4), C6S3 = 1.706(4), C6S4= 1.701(4), C9S5 = 1.702(4), C9S6 = 1.702(4) ,Corros.Sci.2013,73,L.K. Li, L.L. Wei, X.Q. Si, L.Y. Fan, C.H. Wang, Hou, .Chim.Acta2013,405which ermediate n single and double X.M.Zhang,Coord. Chem.Rev. 2005,249,lengths and suggest considerable delocalization of J.Song, B.C.Wang, H.M. Hu,L.Gou, Q.R.Wu,X.L. Y.Q. Shangguan, F.X. Dong, G.L. Xue,J.Song, B.C.Wang, H.M. Hu,L.Gou, Q.R.Wu,X.L. Y.Q. Shan