Patent GB-935716-A (GB)
Title: Complexes of transition metals and the production thereof
IPC: C07F17/00
Filed: 1961-04-19
Abstract: Dimers and trimers of 1,3-diolefins are obobtained from the diene in the presence, as catalysts, of carbon monoxide free complexes of transition metals made by reacting a compound of a transition metal with an organometallic compound of Group I to III of the Mendel<\>eeff Periodic Table in the presence of an electron donator (see Group IV(b)).  Examples 10-13 inclusive describe the preparation of vinyl cyclohexene, cyclooctadiene, 3-methyl heptatriene and cyclododecatriene from butadiene. Examples 16, 17 and 18 refer to the dimerization of butadiene to cyclooctadiene using respectively tetrakis (triphenyl phosphine) nickel, Ni[P(C6H5)3]4, bis(triphenylphosphine) nickel, Ni[P(C6H5)3]2, and cyclooctadiene nickel bis (triphenylphosphine) C8H12Ni[P(C6H3)3]2.ALSO:Butadiene may be polymerized using as catalyst a carbon monoxide free complex of a transition metal prepared by reacting a compound of a transition metal with an organometallic compound of Group I to III of the Mendel<\>aeeff Periodic Table in the presence of an electron donator. Examples 15 and 25 refer to the use as catalyst of (a) a complex of vanadium acetylacetonate and triphenyl phosphine, and (b) a complex of vanadyl acetylacetonate and #c,#c1-di-pyridyl.ALSO:The invention comprises carbon monoxide free complexes of transition metals which complexes are made by reacting organometallic compounds of Group I to III of Mendel<\>aeeff Periodic Table with compounds of the transition metals in the presence of electron donators.  The preferred metals are those of Group I, IV, V, VI, VII and VIII of the Mendel<\>aeeff Periodic Table, especially iron group metals, vanadium, chromium and manganese.  Suitable electron donators include compounds containing C=C and C=C bonds, and groups of atoms with non-linking electron pairs.  Cyclic olefins, conjugated olefins, acetylenes, diketones, and alkyl and aryl compounds of Group Va elements are especially effective.  The transition metal compound may contain either inorganic or organic radicals as anions: acetyl acetonates, acetoacetic ester enolates, alcoholates, salts of weak organic acids and dimethyl gloxime compounds are specified.  Group I to III organometallic compounds specified include butyl lithium, diethyl zinc, ethyl- or phenyl-magnesium halides, trialkyl aluminium compounds and alkyl aluminium alkoxides.  Suitable solvents include aliphatic, alicyclic or aromatic hydrocarbons (hexane, cyclohexane and benzene), ethers and cyclic ethers.  The following are prepared [the "(O)" indicates zerovalency]:  Ex 1 di(cyclooctadiene-1:5) nickel, (C8H12)2  Ni; Ex 2 cyclooctatetraene nickel-(O),(C8H8)Ni;  Ex 3 all-transcyclododeca- (1,5,9)- trienecentro-nickel-(O), C12H18Ni; Ex 6 cyclooctadienenickel-(O)- acetylacetone, C13H20O2Ni;  Ex 10 a complex from cobalt acetyl acetonate and phenyl acetylene;  Ex 11 a complex from iron acetyl acetonate and phenyl acetylene;  Ex 12 a Fe-acetyl acetonate-triphenyl phosphine complex;  Ex 13 a Co-acetylacetonate-triphenyl phosphine complex;  Ex 14 a Cracetylacetonatetriphenylphosphine complex;  Ex 15 a V-acetylacetonate-triphenylphosphine complex;  Ex 16 tetrakis (triphenylphosphine) nickel, Ni[P(C6H5)3]4;  Ex 17 bis(triphenylphosphine) nickel, Ni [P(C6H5)3]2;  Ex 18 cyclooctadiene nickel bis-(triphenylphosphine), C8H12Ni[P(C6H5)3]2;  Ex 22 trans-stilbene nickel bis(triphenylphosphine), C14H12Ni[P(C6H5)3]2; Ex 23 tris(trans-stilbene) nickel, Ni(C14H12)3;  Ex 24 bis(phosphorous acid tripiperidide) nickel, Ni[P(NC5H10)3]2;  Ex 25 a complex from vanadyl acetylacetonate and a ,a 1-dipyridyl;  Ex 26 tetrakis (triphenylphosphine) cobalt, Co[P(C6H5)3]4;  Ex 27 Co(C8H8)x where x is from 1 to 2;  Ex 28 tetrakis (cyclooctatetraene)dititanium, Ti2(C8H8)4;  Ex 29 tris (cyclooctatetraene) dititanium, Ti2(C8H8)3;  Ex 31 tetrakis (triphenylphosphine) palladium, Pd[P(C6H5)3]4;  Ex 32 tetrakis (triphenylstilbene) nickel, Ni [Sb(C6H5)3]4;  Ex 33 tetrakis (triphenylarsine) nickel, Ni [As(C6H5)3]4;  Ex 34 di-hexamethylbenzene-chromium (O), Cr(C12H18)2;  Ex 35 cobalt acetyl acetonate-bis(triphenylphosphine), Co(C5H7O2)[P(C6H5)3]2;  Ex 36 copper acetyl acetonate-bis(triphenylphosphine), Cu(C5H7O2)[P(C6H5)3]2; and  Ex 37 tris(cyclooctatetraene dimanganese, Mn2(C8H8)3.