摘要
利用由化学还原剂BPK引发的电子迁移催化反应(ETC)合成了两个系列八种新的三核钴簇合物p-RC_6H_4CCo_3(CO)_(9-n)L_n(L=PPh_3,n=1;L=P(OEt)_3,n=2)。用m.p.、元素分析、IR及~1H NMR对簇合物进行了表征。对簇合物在Pt电极上的循环伏安(CV)研究表明,p-RC_6H_4CCo_3(CO)_9及PPh_3单取代物在室温下均经历一个可逆的单电子过程。p-RC_6H_4CCo_3(CO)_9的E_(1/2)与R的σ_m的线性关系表明R通过诱导效应影响簇合物的氧化还原性。取代簇合物的还原电势相对于母体簇合物的负移表明P的配位增大了CCo_3上的电荷密度,导致簇合物难被还原。
Eight new tricobalt clusters p-RC_6H_4CCo_3 (CO)_(9-n)L_n(L=PPh_3, n=1; L=P (OEt)_3, n=2) have been prepared by means of chemically induced Electron-Transfer-Catalysis (ETC) reaction. The clusters were characterized by m. p., elemental analysis, IR and ~1H NMR spectra. Cyclie voltammetric study of the olusters p-RC_6H_4CCo_3(CO)_(9-n)L_n(n=0, 1, 2) on Pt electrode in acetone were described. n=0 and 1 clusters showed reversible mono-electron process, but n=2 derivatives showed quasi-reversible process. A Linear relationship between E(1/2) of n=0 clusters and σ_m of R groups indicated that redox properties of the clusters were affected by inductive effect of the R group. A cathodic reduction potential shift of L substituted derivatives vs the parent clusters showed that coordination of L to Co resulted in the increase of charge density on CCo_3 unit, wkioh made the cluster hard to reduce.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1992年第5期444-448,共5页
Acta Chimica Sinica
基金
国家自然科学基金资助的项目
