Patent GB-891596-A (GB)
Title: Manufacture of manganese carbonyl
IPC: C01G45/04
Filed: 1958-12-16
Abstract: Manganese carbonyl is produced by reacting a manganous compound simultaneously with CO and a Group Ia or IIIa element, a stable organo compound of a Group IIb or IIIa element, or a hydride of a Group Ia, IIa or IIIa element.  Manganous compounds specified are halides, phosphates, sulphates, sulphites, nitrates, fluosilicates, carbonates, acetate, benzoate, citrate, formate, lactate, oxalate, malonate, valerate, naphthenate, oleate, acetylacetate, toluate, decanoate, methylmercaptide and oxide, sulphide, alkoxide, and phenate.  The manganese compound may be employed in finely-divided form.  The Group Ia metal may be Na, K, Li, Rb, or Cs, used in solid or liquid form, the Group IIIa element may be B, Al, Ga, In or Tl, used in finely-divided form or as an Al-Cu-Zn alloy, the Group IIb organo-compound may be of Zn, Cd or Hg and may be diisopropylzinc, diethylzinc, dimethylzinc, dibutylzinc, diamylzinc, dihexylzinc, dioctylzinc, methylethylzinc, ethyl-n-propylzinc, isopopyl-n-butylzinc, n-heptyl-n-octylzinc, ethylzinc bromide, chloride, iodide or hydride, n-butylzinc bromide or hydride, dicyclohexylzinc, sodium zinc triethyl, diphenylzinc, dibenzylzinc, diethylcadmium, diethylmercury, ethylcadmium chloride, ethylmercury iodide, diphenylcadmium or dibenzyl mercury.  The Group IIIa organo-compound may be trimethylboron, triethylboron, ethylboron difluoride, sodium tetraethylborate, trimethylaluminium, triethylaluminium, methyldiethylaluminium, tripropylaluminium, dimethylhexylaluminium, methylaluminium dihydride, triisobutylaluminium, diisobutylaluminium hydride, octylaluminium dihydride, sodium aluminium tetraethyl, lithium aluminium tetraethyl, potassium aluminium triethyl hydride, sodium aluminium tetrabutyl, potassium aluminium dioctyl dihydride, dimethylaluminium chloride, ethylaluminium dichloride, ethylaluminium sesquichloride, trimethylgallium triethylgallium, methyldiethylgallium, tripropylgallium, trioctylgallium, triisobutylgallium, trimethylindium, triethylindium, tripropylindium, triisobutylindium, triphenylaluminium, sodium aluminium diethylacetylide, cyclohexyldiethylaluminium, tribenzylaluminium, triethylthallium, and triphenylthallium.  The hydrides may be of Na, Li, K, Rb, Ca, Mg, Ba, Sr, B, Al, Ga or In, and include diborane, sodium aluminium hydride, sodium borohydride, magnesium aluminium hydride, lithium aluminium hydride, and lithium borohydride.  Where solid, the hydride may be used in finely-divided form.  The manganous compound and the element or compound may be passed into a reaction vessel and pressurized with CO, the reaction mixture may be stirred and heated, and the reaction may be conducted in presence of an inert liquid medium.  The pressure may range from subatmospheric to 4,000 atmospheres.  The manganese carbonyl may be recovered by distillation or sublimation or by separation of the by-products, leaving the product in the inert liquid medium, followed by recovery of the product by concentration and filtration.  In Example I, a mixture of manganous acetate, sodium of particle size less than 50 microns, and the dimethyl ether of diethylene glycol is pressurized with 3,500 p.s.i.g. of CO, the mixture is heated to 165 DEG C. with continuous agitation for 3 hours, and, after cooling to 30 DEG C., the manganese pentacarbonyl dimer is recovered by steam distillation.  Examples II and III are similar using manganous acetylacetate, potassium and hexane, and using manganese ethoxide, sodium and pyridine.  Example IV uses manganous acetylacetate, finely-divided aluminium and toluene, Example V manganous acetate, aluminium and benzene, Example VI manganous chloride, aluminium and no diluent, Example VII manganous ethoxide, aluminium turnings and pyridine, Example VIII manganous acetylacetate, triethyl aluminium and benzene initially in a nitrogen atmosphere, the reaction mixture being quenched with dilute hydrochloric acid, Example IX is similar using a 6-hour reaction period, Example X is similar using diethyl ether, Example XI is similar using a temperature of 100 DEG C. for 3 hours, Example XII is similar using manganous chloride, Example XIII is similar using manganous acetate, Example XIV is similar to Example XIII using a greater quantity of diethyl ether and a reaction time of 6 hours, Example XV is similar using anisole, Example XVI uses manganous acetylacetate, diethylaluminium hydride and diethyl ether, Example XVII uses manganous sulphide, trimethylthallium (or triphenylgallium or tribenzylindium with diethyl ether) and pyridine, Example XVIII uses manganous acetate, diethylzinc and diethyl ether, quenching being effected with dilute hydrochloric acid, Example XIX is similar to Example XVIII using anisole, Example XX uses manganous formate, ethylzinc chloride and benzene, Example XXI uses manganous acetate, diethylcadmium and mesitylene, and Example XXII uses manganous chloride, sodium hydride and tetrahydrofuran.  Example XXIII illustrates the increased yield obtained by increasing the proportion of triethylaluminium.  Numerous other organic diluents are specified. In preparing alkali metal dispersions, the same organic liquids may be used, with the addition of dispersing agents such as oleic acid, polyethylene, carbon black or alcohols.  Hydrogen may be added to the CO.  The Group IIIa element may be amalgamated, or salts such as calcium iodide, cuprous chloride, zinc chloride or aluminium chloride may be added.