Patent GB-946674-A (GB)
Title: Improvements in or relating to compounds of zerovalent elements of group vi(b) of the periodic table
IPC: C07F9/90
Filed: 1960-02-12
Abstract: Complex carbonyls are obtained by reacting at elevated temperature a compound of trivalent phosphorus, antimony, arsenic or bismuth with a carbonyl of chromium, molybdenum, tungsten and uranium.  The products are of formula (MH3)nZCO6-n where M is P, As or Bi and Z is Cr, Mo, W or U, n being from 1 to 5.  Specified compounds of trivalent phosphorus, antimony, arsenic or bismuth include the trichlorides, triiodides, trifluorides and tribromides of the said elements. The reaction is preferably carried out by refluxing the reactants in a high boiling organic solvent, e.g. bis-(2-ethoxyethyl) ether, trimethylene glycol, bis-(2-methoxy-ethyl) ether or tetrahydrofuran. The products are useful as motor fuel additives, as lubricant additives, as catalysts in the Oxo synthesis or Acrylate synthesis, as polymerization catalysts and as active components of pesticidal or herbicidal compositions.ALSO:The invention comprises a product obtained by reacting at elevated temperature a compound of a trivalent element selected from phosphorus antimony, arsenic and bismuth with a compound of a zerovalent metal selected from chromium. molybdenum, tungsten and uranium.  The zerovalent metal compound may suitably be a carbonyl compound e.g. a hexacarbonyl of the specified metal, dibenzene chromium, dicumene chromium, or an arene chromium tricarbonyl such as benzene chromium tricarbonyl, 1,2,4,5,- tetramethyl benzene chromium tricarbonyl or 1,3,5-triisopropylbenzene chromium tricarbonyl.  Preferred products are those having the structure: <FORM:0946674/C2/1> wherein M is P, As, Sb or Bi, Z is Cr, Mo, W, or U, n is a whole number from 1 to 5 inclusive and, R1, R2, and R3 are the same or different radical selected form hydrogen, halogen, alkyl, cyanoethyl aryl, alkoxy or aryloxy. When n is greater than 1 M can be the same or different element of the indicated group. The term aryl is intended to include haloaryl radicals.  Suitable trivalent compounds are the trihalides, tertiary phosphines, phosphites, arsines, arsenites, stibines, stibites, bismuthines and bismuthites. The products may be obtained by heating the reactants in the presence or absence of a solvent and at atmospheric or superatmospheric pressure.  Preferably the reactants are refluxed in a high boiling organic solvent, e.g. bis(2-ethoxyethyl)ether, trimethylene glycol, bis(2 - methoxy - ethyl)ether or tetrahydrofuran. It is also possible to further react a product of the invention with a compound of the trivalent element so that more of the carbonyl groups are replaced and the value of n in the above formula increases.  Examples are given for the production of triphenyl phosphine chromium molybdenum and tungsten pentacarbonyls, tris (2 - cyanoethyl) phosphine chromium pentacarbonyl, triphenyl phosphite chromium pentacarbonyl, triphenyl phosphite chromium pentacarbonyl, bis (triphenyl phosphite) chromium tetracarbonyl, tris (triphenyl phosphite) chromium tricarbonyl, bis (tri-n-butyl phosphite) chromium tetra-tricarbonyl, triphenyl arsine chromium pentacarbonyl and bis (triphenyl phosphine) chromium tetracarbonyl. The products are useful as motor fuel additives, lubricant additives, as catalysts in the "Oxo" synthesis or "Acrylate" synthesis, as polymerization catalysts or cocatalysts and as active components of biologically active compositions, e.g. pesticides or herbicides (see Division A5).ALSO:A pesticidal or herbicidal composition contains as active ingredient a product obtained by reacting at elevated temperature a compound of trivalent phosphorus, antimony, arsenic, or bismuth with a compound of a zerovalent metal selected from chromium, molybdenum, tungsten and uranium (see Division C2).  The zerovalent metal compound may suitably be a carbonyl, e.g. a hexacarbonyl of the specified metal, an arene chromium tricarbonyl, e.g. benzene (1,2,4,5 - tetramethylbenzene - or 1,3,5 - triisopropylbenzene -) chromium tricarbonyl, dibenzene chromium or dicumene chromium.  Preferred products are those having the structure <FORM:0946674/A5-A6/1> wherein M is P, As, Sb or Bi, Z is Cr, Mo, W or U, n is a whole number from 1 to 5 and R1, R2 and R3 are the same or different radicals selected from hydrogen, halogen, alkyl, cyanoethyl, aryl (including haloaryl), alkoxy or aryloxy.  When n is greater than 1 M can be the same or different element of the specified group.  The composition may be in conventional liquid or solid form and other pesticidal, fungicidal, or herbicidal compounds such as organic phosphates and chlorinated hydrocarbons may be present.  Specified diluents include various solid carriers, water, benzene, toluene, xylene, chlorinated benzene, acetone, cyclohexanone, carbon disulphide and carbon tetrachloride and a surface active agent may be present.  Specified forms are powders, granules, emulsifiable concentrates and slurries.