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The reaction of mer-tricarbonyl-nitrosyl-bis(triisopropylphosphite)tungsten hexafluorophosphate (1a) with MeMgl or Bu 4 NI 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 -  , OCH 3  -  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 NaBH 4  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.

zeitschrift für naturforschung b

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