Patent GB-958940-A (GB)
Title: Process of preparing organic derivatives of group vib metal carbonyl compounds and the derivatives so prepared
IPC: C06B23/00
Filed: 1959-09-14
Abstract: The invention comprises cycloheptatriene-Group VIB metal-tricarbonyls (product I) of formula: <FORM:0958940/C2/1> ditropyl-Group VIB metal tricarbonyls, ditropyl bis (Group VIB metal tricarbonyl) compounds (product II) and arene Group VIB metal tricarbonyl compounds (product III).  The Periodic Table used is the Deming revision. (Ditrophyl-dicycloheptatrienyl, formula: <FORM:0958940/C2/2> They may be obtained by reacting a tropylium Group VI-B metal bicarbonyl cation with an anion according to the reaction: <FORM:0958940/C2/3> in which M is chromium, molybdenum or tungsten.  The product obtained is dependent upon the particular anion Y- which is used. The reaction may be carried out at a temperature between -20 DEG C. and 100 DEG C., desirably under an inert atmosphere (nitrogen, argon, krypton, neon) and in the presence of an inert solvent. Solvents specified include high boiling saturated hydrocarbons, aromatic hydrocarbons, ethers including cyclic ethers, esters and silicone oils. Specified cations in the tropylium-Group VI-B metal-tricarbonyl cations include fluoride, chloride, bromide, iodide, sulphate, tetrachloromercurate, tetrachlorogallate, hexachloroplatinate and picrate, the perchlorate and fluoborate being preferred.  Product I (cycloheptatriene-Group VI-B metal-tricarbonyl) may be produced when the attacking anion is methoxy, ethoxy, propoxy, butoxy, phenoxy, carboxyethyl, carboxymethyl, ethylthio, methylthio, phenylcarbonyl, methylcarbonyl, ethylcarbonyl or phenylthio. Product II (the ditropyl compounds, produced by coupling) may be produced when the anion is <\>bCN, <\>bOH, <\>bOOC-OR, <\>bOOCR, <\>bNHR and <\>bR where R is C1-C7 alkyl, phenyl, biphenyl or naphthyl, or by reaction with a non-ionic Lewis base capable of donating a pair of electrons to the cation, such as methylamine, ethylamine, phenylamine and dimethylamine. Product III (the arene-Group VI-B metal-tricarbonyl) is formed by the expulsion of a CH grouping from the cycloheptatriene ring, probably according to the equation: <FORM:0958940/C2/4> Anions which react in this manner are: <FORM:0958940/C2/5> Examples of the production of all three products are given in the Specification.  Specifications 856,354 and 894,852 are referred to.ALSO:Cycloheptatriene Group VIB metal tricarbonyls of formula <FORM:0958940/C3/1> ditropyl Group VIB metal tricarbonyls, ditropyl bis Group VIB metal tricarbonyl compounds of formulae <FORM:0958940/C3/2> and arene Group VIB metal tricarbonyl compounds may be used as drying agents in paints, varnish, printing inks, drying oil type synthetic resins and oil enamels.  Metals specified are chromium, molybdenum and tungsten. The above compounds may be used in residual fuels, distillate fuels and diesel fuels to reduce smoke and/or soot formation and in gasolines as anti-knock agents.  Other anti-knock agents, e.g. tetraalkyl leads, and scavengers, e.g. ethylenedichloride, ethylene dibromide, tricresylphosphate and trimethylphosphate may also be present.  Specifications 856,354 and 894,852 are referred to.ALSO:Cycloheptatriene-Group VIb metal-tricarbonyls of formula <FORM:0958940/C3/1> ditropyl-Group VIb metal tricarbonyls, ditropyl bis (Group VIb metal tricarbonyl) compounds of formulae <FORM:0958940/C3/2> and arene-Group VIb metal tricarbonyl compounds may be used in vacuum plating by thermal decomposition.  The metal film may be deposited on glass cloth.  Metals specified are chromium, molybdenum, and tungsten.  Specifications 856,354 and 894,852 are referred to.