In this study,we present a convenient method to obtain two types of novel tetra-substituted Fe/Se salts through a dehalogenation reaction,aiming to advance research on mimicking the FeⅡFeⅡ oxidation state of[FeFe]-H...In this study,we present a convenient method to obtain two types of novel tetra-substituted Fe/Se salts through a dehalogenation reaction,aiming to advance research on mimicking the FeⅡFeⅡ oxidation state of[FeFe]-H_(2) ases.Initially,by treating[Fe_(2)(μ-SeBn)_(2)(CO)_(4)(dppv)](Bn=CH_(2)C_(6)H_(5),dppv=cis-1,2-bis(diphenylphosphino)ethylene)with one equivalent of dppv under UV and reflux conditions,the neutral FeIFeI and FeⅡFeⅡ precursors[Fe_(2)(μ-SeBn)_(2)(CO)_(2)(dppv)_(2)](1)and[Fe_(2)(μ-SeBn)_(2)(μ-Se)(CO)_(2)(dppv)_(2)](2)were successfully isolated in good yields.Subsequently,1 underwent dehalogenation reactions with halocarbons(such as CCl_(4) and CBr4)or I_(2),leading to the formation of tetra-substituted salts[Fe_(2)(μ-SeBn)_(2)(μ-X)(CO)_(2)(dppv)_(2)]+(X=Cl,Br,and I)([3]Cl,[4]Br and[5]I_(3)).GC-MS analysis of the reaction with carbon tetrachloride detected the formation of the homo-coupled product CCl_(3)-CCl_(3)(m/z=235),indicating the presence of a CCl_(3)·species.Notably,2 also exhibited intriguing reactivity with R-X and I_(2).Unlike 1,the reaction of 2 with RX or I_(2) involved cleavage of the C-Se bond,leading to the isolation of[Fe_(2)(μ-SeBn)(μ-Se_(2))(CO)_(2)(dppv)_(2)]+X-(X=Cl,Br,I_(3))([6]Cl,[6]Br and[6]I_(3))in good yields.The reaction involved debenzylation of 2 and was confirmed by GC-MS detection of C6H5CH_(2)CCl_(3)(m/z=208)in the reaction with CCl_(4),suggesting a radical pathway.展开更多
基金the Natural Science Foundation of Shandong Province(No.ZR2020MB019)Introduction and Cultivation Project for Young Innovative Talents in Shandong Provincial Colleges and Universities for financial support.
文摘In this study,we present a convenient method to obtain two types of novel tetra-substituted Fe/Se salts through a dehalogenation reaction,aiming to advance research on mimicking the FeⅡFeⅡ oxidation state of[FeFe]-H_(2) ases.Initially,by treating[Fe_(2)(μ-SeBn)_(2)(CO)_(4)(dppv)](Bn=CH_(2)C_(6)H_(5),dppv=cis-1,2-bis(diphenylphosphino)ethylene)with one equivalent of dppv under UV and reflux conditions,the neutral FeIFeI and FeⅡFeⅡ precursors[Fe_(2)(μ-SeBn)_(2)(CO)_(2)(dppv)_(2)](1)and[Fe_(2)(μ-SeBn)_(2)(μ-Se)(CO)_(2)(dppv)_(2)](2)were successfully isolated in good yields.Subsequently,1 underwent dehalogenation reactions with halocarbons(such as CCl_(4) and CBr4)or I_(2),leading to the formation of tetra-substituted salts[Fe_(2)(μ-SeBn)_(2)(μ-X)(CO)_(2)(dppv)_(2)]+(X=Cl,Br,and I)([3]Cl,[4]Br and[5]I_(3)).GC-MS analysis of the reaction with carbon tetrachloride detected the formation of the homo-coupled product CCl_(3)-CCl_(3)(m/z=235),indicating the presence of a CCl_(3)·species.Notably,2 also exhibited intriguing reactivity with R-X and I_(2).Unlike 1,the reaction of 2 with RX or I_(2) involved cleavage of the C-Se bond,leading to the isolation of[Fe_(2)(μ-SeBn)(μ-Se_(2))(CO)_(2)(dppv)_(2)]+X-(X=Cl,Br,I_(3))([6]Cl,[6]Br and[6]I_(3))in good yields.The reaction involved debenzylation of 2 and was confirmed by GC-MS detection of C6H5CH_(2)CCl_(3)(m/z=208)in the reaction with CCl_(4),suggesting a radical pathway.
