The substitution reaction of quinin e by the 18types of heteropoly comple xes,for these formed compounds are Keggin structure and the molecular f ormulas arXM 11 O 39 M’ (OH) 2 6- (X =Si,Ge,P;M=Mo or W;M’ =Co,Ni,Cu),was studied by the means of phase tra nsfer.The results of characterization that were accomplished by UV and ESR indicated that the quinine does f orm the chemical bond with the hetrop oly ligands.Spectral experiment demonstrated that the structure held the same when the heteropoly comple x contained Cu 2+ was reacted with qui-nine,while the heteropoly complex c ontained Ni 2+ resulted in the changing of the structure.Such a result of op-tical rotatory opticity testified t hat quinine reacting with heteropoly acid contained transitional metals could form a kind of new complexes which were opti cal rotation.
Eight new complexes were synthesize d for the first time.The compounds which have the general formula K x H 2 [PM(OH 2 )Mo 7 W 2 V 2 O 39 ]·nH 2 O(M=Cr 3+ ,Mn 2+ ,Fe 3+ ,Co 3+ ,Ni 2+ ,Cu 2+ ,Zn 2+ ,Cd 2+ ;x=4or 5)were de-termined by conductance titration a nd elemental analysis.The analysis of IR,UV,XRD and ESR show that the products hold the Keggin structure a nd TG-DTA,IR,XRD at various tempera tures and water solubility test also give the evidences that the range of pyrolysis temperature is 300～350℃.T he study on the substitutional reaction of coordinated water by optical ligand quinine shows that the S N 2nucleophilic substitution occure s when Ni is con-tained in the compound and S N 1nucleophilic substitution occure s when Cu is contained.These also con firmed that the transitional metals are in the in ner sphere of the complexes.
ZHOU Bai-Bin *,1,2 WEI Yong-De 1 LI Zhong-Hua 1 ( 1 Department of Applied Chemistry,Ha rbin Institute of Technology ￡?Harbin￡±￡ì￡°￡°￡°￡±￡(c)( 2 Department of Chemistry,Harbin Normal University￡?Harbin￡±￡ì￡°￡°￡?￡°￡(c) The air-solid interface reaction of Ce,Lu with K10 H 3[Gd (SiMo 4 W￡*O￡3￡1￡(c) 2]through chemistry-heated permeation is reported for the fi rst time￡(r)The permeated complex is characterized by ICP and the result shows tha t the mini mum Ce,Lu can permeate into the inner sph ere of K 10 H ￡3 ￡?Gd ￡¨SiMo ￡′ W ￡* O ￡3￡1 ￡(c) 2]The IR ,XRD patterns give the eviden ce that after permeation the comple x still keeps the Keggin structure,howe ver,its crystal structure is different from the complex before permeation￡(r)The cond uctivity of the permeated complex has been measured with the four-electr ode method and the data show that the co nductivity of the complex after permeation is 10 6 times higher than that of the sample before permeation and reaches ￡′￡(r)84 6×10 -1 S·cm -1 ￡(r)These indicate that the permeated c omplex is a good solid electrolyte and further appli cations are also expected￡(r)
A new kind of Anderson type chromium molybdates containing the rare earth elements are synthesized, which have the general molecular formula of (NH4)6[CrMo5Ln(OH2)2O24H6]·xH2O (Ln=La,Ce,Pr,Nd,Sm,Gd and Yb). The components of theseheteropoly complexes are determined by chemical elemental analysis, ICP and TG DTA. And IR, UV, ESR,XPS and 1H NMR are also applied to characterize the complexes as well. The results indicate that the structures of these complexes are Anderson B type and the rare earth elements are in the inner sphere of the heteropoly salts. The thermal stabilities of these complexes studied by TG DTA show that the range of pyrolysis temperature is between 490℃and 500℃.
