Redoxreaktivität Phosphido‐verbrückter Heterodimetallkomplexe

Redox Reactivity of Phosphido‐Bridged Heterodimetallic Complexes The metal‐metal bond in ( 3a,b,e ) [LCO: RPh ( a ), Cy (e); LPMe 3 : RPh ( b )] is cleaved reductively, oxidatively, and by nucleophiles by using Na[HBEt 3 ], bromine or iodine, and PMe 3 , respectively. The action of PMe 3 on 3a affords Me 3 P(OC) 4 Mn – PPh 2 – Fe(CO) 4 ( 5 ), which is photolyzed to give 3b . While the reduction of 3a can be regarded as a nucleophilic bond opening functionalizing only manganese, oxidation of 3a,b with halides results in the formation of the complexes XMn(CO) 4 – PPh 2 – Fe(X)(CO) 3 L ( 4a – d ) [LCO: XI ( a ), Br ( c ); LPMe 3 : XI ( b ), XBr ( d )], which provide two functionalized metals. To elucidate the redox behavior of 3a cyclovoltammetric investigations were carried out. They indicate a complex reaction scheme including reactions of higher order.