Chemische Effekte der Nitrosylsubstitution in hexakoordinierten Carbonylwolfram-Verbindungen/ Chemical Effects of Nitrosyl Substitution in Hexacoordinated Carbonyl Tungsten Complexes

Abstract

Abstract The reaction of mer-tricarbonyl-nitrosyl-bis(triisopropylphosphite)tungsten hexafluorophosphate (1a) with MeMgl or Bu4NI affords tricarbonyl-iodonitrosyl-(triisopropylphosphite)tungsten (2). Similarly, a carbonyl group of la can be replaced by a fluoride ion resulting in transdicarbonyl- fluoronitrosyl-bis(triisopropylphosphite)tungsten (3). Oxygen nucleophiles like OPh- , OCH3 - or OH- either substitute or attack a carbonyl group in la and cause formation of dicarbonyl-nitrosyl-bis(triisopropylphosphite)tungsten phenoxide. methoxide or formate derivatives (4, 5 or 7). respectively. Nitrite ions react with la under CO substitution and bind as nitro ligands to the tungsten center. Addition of equivalent amounts of MeLi, PhLi and NaBH4 to la leads to the formation of tricarbonyl-nitrosyl-(triisopropylphosphite)tungsten methyl and hydrido compounds (8a, 11a) as well as to dicarbonylnitrosyl-bis(triisopropylphosphite)tungsten methyl, phenyl and hydrido complexes (8b, 10 and 11b ) . In the presence of an excess of MeLi., la is transformed to a β-diketonate derivative 9.