Patent GB-894852-A (GB)
Title: Cycloheptatrienyl metallocarbonyl compounds
IPC: C03C17/10
Filed: 1958-12-08
Abstract: Cycloheptatrienyl metallocarbonyl compounds of formula <FORM:0894852/III/1> where M1 and M2 are metals from Group VIb-VIII of the Periodic Table (Deming), R1 and R2 are monovalent hydrocarbon groups, b and c are 0 or integers from 1 to 6, d and f are integers from 1 to 3, t is 0 or 1, and M1 and M2 have an electron configuration ranging from two less than up to and including the electron configuration of the next higher rare gas, may be used as additives to diesel fuels and jet fuels and burning oils to reduce smoke and soot, as antiknock agents in internal combustion engine fuels and as lubricity improvers in lubricating oils.  It is preferred that M1 and M2 are iron or manganese when the compounds are used as antiknock agents, and molybdenum when used as antiwear additives. Scavengers (halohydrocarbon or phosphorus compounds), deposit-modifying agents (phosphorus or boron compounds) and other antiknock agents (e.g. tetraethyl lead) may also be present. Typical compounds are 1, 11-bis-(2, 4, 6-cycloheptatrienyl molybdenum tricarbonyl) and 2-methyl-31-eicosyl-1, 11-di(2,4,6-cycloheptatrienyl tungsten tricarbonyl) ether: many others are specified.  They may be used in a concentration range from about 0,015 to about 10 grams per gallon based on the weight of the metal.ALSO:The invention comprises compounds of the formula <FORM:0894852/IV (b)/1> wherein M1 and M2 are metals from Group VI (B)-VIII of the Periodic Table (Deming), R1 and R2 are monovalent hydrocarbon groups, b and c are 0 or integers from 1 to 6, d and f are integers from 1-3, t is 0 or 1, and M1 and M2 have an electron configuration ranging from two less than up to and including the electron configuration of the next higher gas.  M1 and M2 may be the same or different.  Metals specified include molybdenum, chromium, tungsten (Group VI(B)), manganese, technetium, rhenium (Group VII (B)) and iron, ruthenium, cobalt, rhodium, platinium, iridium, osmium, palladium and nickel (Group VIII). R1 and R2 may contain 1-20 carbon atoms.  Typical compounds of the invention are 2,21-dimethyl-1,11-bis(2,4,6-cycloheptatrienyl chromium tricarbonyl), 2-methyl-31-eicosyl - 1, 11 - di (2, 4, 6 - cycloheptatrienyl tungsten tricarbonyl) ether, 2-2-tert.butyl-1,11-di-2,4,6-cycloheptatrienyl nickel carbonyl) ether, 2-ethyl - 1, 11 - bis (2, 4, 6 - cycloheptatrienyl molybdenum tricarbonyl: many others are specified.  They may be prepared by reacting a 1,11-bis(2,4,6-cycloheptatrienyl) compound of formula <FORM:0894852/IV (b)/2> with the appropriate metal carbonyl, preferably in excess.  Two to ten moles of metal carbonyl may be used for each mole of the bis-cycloheptatrienyl compound.  The process may be carried out at a temperature between about 75 DEG C. and about 200 DEG C., at atmospheric or higher pressure (up to 500 atmospheres), and under an inert gas atmosphere (nitrogen, helium or argon).  It is preferred to use a non-reactive solvent such as a high boiling saturated hydrocarbon, ether, ester, or a silicone oil. Polymerisation of the bis-cycloheptatrienyl reactant may be prevented by the use of a free-radical inhibitor such as hydroquinone, p-tert. butyl-catechol, p-hydroxy-anisole, 4-amino-1-naphthol, chloranil, 2,4-dinitro-chlorobenzene or dithiocarbonate.ALSO:Metal coatings may be formed on glass, glass cloth, resins or other supports by the thermal decomposition at above 400 DEG C. of a cyclo-heptatrienyl metallo carbonyl compound of formula <FORM:0894852/II/1> where M1 and M2 are the same or different and are metals from Groups VIB-VIII of the Periodic Table (Deming), R1 and R2 are monovalent hydrocarbon groups, b and c are 0 or integers from 1-6, d and f are integers from 1-3, t is 0 or 1 and M1, and M2 have an electron configuration ranging from two less than up to and including the electron configuration of the next higher rare gas.  The metals specified are molybdenum, chromium, tungsten (Group VIB), manganese, technetium, rhenium (Group VIIB) and iron, ruthenium, cobalt, rhodium, platinum, iridium, osmium, palladium and nickel (Group VIII).  The deposition of molybdenum on glass cloth by thermal decomposition of 1, 11-bis (2, 4, 6-cycloheptatrienyl molybdenum tricarbonyl).