1,3-Cyclobutadiene, 1,2,3,4-tetraphenyl-, complexes with

Tetramethyl- or tetraphenyl- (cyclobutadiene)nickel dihalides undergo reductive ligand substitution with nitrogen donor ligands such as 2,2 -bipyridine or 1,4-diaza-1,3-dienes with the addition of sodium metal237. The 2,2/-bipyridyl ligand is readily displaced and reaction of this complex with a variety of olefins and alkynes leads to cycloaddition reactions with the cyclobutadiene ligand. 

These have previously been obtained by electrophilic attack on ene-yl complexes [equation (a) Y = CH(C02Me)2, OMe ch = 1J-C5H5 diene = 1,5-cyclooctadiene]1 or by reaction of the compounds (diene)MBr2 with 57-C5H6Fe(CO)2Br (diene = 1,5-cyclooctadiene or 1,2,3,4-tetraphenyl-l,3-cyclobutadiene).2 An example of the former method is given in which the methoxy-cyclooctenyl derivative is used as the substrate and tetrafluoro-boric acid as the electrophile. The substrate is conveniently prepared and used without isolation, and in this way the reaction takes only a few hours, starting with dichloro(l,5-cycloocta-diene)palladium, prepared as described above. 

Diphenylacetylene with Mo(CO)a (298) in a sealed tube at 160°-170°C produces, in addition to two cyclobutadiene complexes, a yellow compound with the empirical formula [C9(CgH5)gO]Mo(CO)2, the infrared spectrum and chemical properties of which suit the tetraphenyl-cyclopentadienone complex of structure (11). On the other hand, the interaction of 3-hexyne with (CH3CN)gMo(CO)3 yields only the alkyne complex (570). 

We found also that (77-C5H,)V(CO)3PPh3 as well as its niobium analog, when irradiated, underwent substitution of one PPh3 and one CO by tolan. Hence, niobium (and tantalum) complexes of the type are able to attach a third molecule of tolan and transform this to hexaphenylbenzene, unlike the vanadium analog, which transforms just two tolans to tetraphenyl-cyclobutadiene or, if irradiated, combines them with carbon monoxide and produces tetraphenylcyclone. 

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