While thousands of molybdenum and tungsten complexes with isocyanides as co-ligands (M-C≡N-R) exist, homoleptic complexes are scarce. Although known since the 1970s, complexes [M(CNR)6] containing aryl isocyanide groups and zerovalent Cr, Mo and especially W have recently gained some attention due to their attractive properties as very strong photoreductants and their low cost compared to ruthenium or iridium compounds. In presence of an oxidant and an excess of isocyanide RNC, complexes [M(CNR)7] 2+ can be prepared. For example, [Mo(CNMe)7] 2+ was prepared by the oxidation of [Mo(CO)6] with elemental iodine in presence of an excess methyl isocyanide. These compounds represent rare examples of homoleptic sevencoordinate complexes.