Patent GB-902610-A (GB)
Title: Novel organometallic salts
IPC: C10M121/00
Filed: 1960-07-26
Abstract: Greases may be prepared from mineral oils, synthetic esters, such as bis(2-ethyl-hexyl) sebacate, silicone oils, pentaerythritol esters, phosphates such as trioctyl phosphate, silicates such as tetraoctyl silicate and polyphenyl ethers such as bis (m-phenoxyphenyl) ether by using as a gelling or thickening agent an organometallic salt consisting of  (a) a cation of formula [(A-M-B)(X)m]+c wherein M represents a metal from Group IVb, Vb, VIb, VIIb or VIII of the Periodic Table (Deming) other than manganese, A and B each represent a poly-unsaturated carbocyclic nucleus directly bound by at least one carbon atom thereof to M, X is an electron donating p  group, c is an integer from 1 to 3, m is 0, 1 or 2 and (m+c) is 1, 2 or 3, and  (b) an anion derived from an anion of a clay, an aliphatic acid, an aromatic acid bearing a co-ordinating substituent, an oil-soluble organic acid, a non oxidizing nitrogen acid or a polyacid as defined in the Specification.  Lists of suitable cations and anions are given.  In Example IX, a grease is prepared from a bright stock mineral oil and octadecyl ferricinium hectorite salt as gelling agent.  Specifications 602,780, 675,836 and 781,065 are referred to.ALSO:Greases may be prepared from silicone oils, silicates such as tetraoctyl silicate by using as a gelling or thickening agent an organometallic salt consisting of (a) a cation of formula [(A-M-B) (X)m]+c wherein M represents a metal from Group IVb, Vb, VIb, VIIb or VIII of the Periodic Table (Deming) other than manganese, A and B each represent a poly-unsaturated carbocyclic nucleus directly bound by at least one carbon atom thereof to M, X is an electron donating group, c is an integer from 1 to 3, m is 0, 1 or 2 and (m+c) is 1, 2 or 3, and (b) an anion derived from an anion of a clay, an aliphatic acid, an aromatic acid bearing a coordinating substituent, an oil-soluble organic acid, a non-oxidizing nitrogen acid or a polyacid as defined in the Specification.  Lists of suitable cations and anions are given.  In the examples, greases are prepared from methyl phenyl silicone oil using as gelling agent (Example I) ferricinium-hectorite salt: (Example II) n-butyl ferricinium-hectorite salt: (Example III) di-n-propyl ferricinium-hectorite salt: (Example IV) n-hexyl ferricinium-hectorite salt: (Example V) di-mesitylene chromium(I)-hectorite salt: (Example VI) bis(biphenyl)chromium(I)-hectorite salt: (Example VII) di-n-propylferricinium-bentonite salt: and (Example VIII) octadecyl ferricinium-hectorite salt.  Specifications 602,780, 675,836 and 781,065 are referred to.ALSO:The invention comprises organometallic salts consisting of (a) a cation of formula [(A-M-B)(X)m]+c wherein M represents a metal from Group IVb, Vb, VIb, VIIb or VIII of the Periodic Table (Deming) other than manganese, A and B each represent a poly-unsaturated carboxylic nucleus directly bound by at least one carbon atom thereof to M, X is an electron donating group, c is an integer from 1 to 3, m is 0, 1 or 2 and (m + c) is 1, 2 or 3, and (b) an anion derived from an anion of a clay, an aliphatic acid, an aromatic acid bearing a coordinating substituent, an oil-soluble organic acid, a non-oxidising nitrogen acid or a polyacid as defined in the Specification.  The nuclei represented by A and B may be the same or different and may be aromatic or contain a cyclopentadiene structure.  Typical cations are (R being a cyclopentadienyl group): (R-Ti-R)+1, (R-Ti-R)+2, (R-V-R)+1, (R-V-R)+2, (R-Cr-R)+1, (R-Fe-R)+1 (i.e. ferricinium), (R-CO-R)+1 (i.e. cobalticinium), (R-Ni-R)+1 (i.e. nickelocinium), R-Zr-R)+2, (R-Nb-R)+3, (R-Ru-R)+1, (R-RH-R)1+, (R-Ta-R)+3 and (R-Ir-R)+1 and the cations derived from oxidation of the following compounds: bis-(acetylcyclopentadienyl) - iron, bis - (beta-chloropropionylcyclopentadienyl)-iron, bis(acryloylcyclopentadienyl) iron, bis(ethylcyclopentadienyl)iron, bis(dimethylcyclopentadienyl)iron, (n - cyclohexylcyclopentadienyl) (isopropylcyclopentadienyl) nickel, bis(ethylcyclopentadienyl)cobalt and bis (indenyl)cobalt.  Many others are specified.  Cations containing an electron donating group include: (R-Ti-R)(OH)+1, (R-MO-R) (Cl)2+1, (R-MO-R)(Cl)+1, and (R-Ta-R)(Cl)2+1.  The cations may contain aromatic nuclei such as benzene, naphthalene, anthracene, acenaphthene, phenanthrene, chrysene, toluene, xylene, cumene, pyrene, mesitylene and ethylbenzene.  Such cations may be obtained by the oxidation of compounds such as bis(phenyl)chromium, bis(biphenyl) chromium, (biphenyl)phenyl chromium and bis (phenyl)cobalt.  The cations may be prepared by first forming the neutral organometallic compound and oxidising using air, chlorine or silver salts.  A long list of suitable anions is included in the Specification.  The salts of the invention may be used as thickening and gelling agents in the preparation of greases (see Groups III and IV(a)) and as catalysts. Specifications 602,780, 675,836 and 781,065 are referred to.