Oligomerization and cross-oligomerization of terminal alkynes catalyzed byorganoactinide complexes

Various organoactinides of the type Cp*(2)An(C=CR)(2) (Cp* = C5Me5; An = Th , U) have been synthesized from the corresponding Cp*(2)AnMe(2) complexes b y addition of an equimolar amount or an excess of the corresponding termina l alkyne. Attempts to trap the mono(acetylide) complexes Cp*(2)An(C=CR)(Me) were successful for only the transient species Cp*U-2(C=C(i-Pr))(Me). The bis(acetylide) complexes are active catalysts for the linear oligomerizatio n of terminal alkynes HC=CR. The regioselectivity and the extent of oligome rization depend strongly on the alkyne substituent R, whereas the catalytic reactivities are similar for both organoactinides. Reaction with tert-buty lacetylene regioselectively yields the 2,4-disubstituted 1-butene-3-yne dim er, whereas (trimethylsilyl)acetylene is regioselectively trimerized to (E, E)-1,4,6-tris(trimethylsilyl)-1,3-hexadiene-5-yne, with small amounts (3-5% ) of the corresponding 2,4-disubstituted 1-butene-3-yne dimer. Oligomerizat ion with less bulky alkyl- and aryl-substituted alkynes produces a mixture of oligomers. Cross-oligomerizations reactions induce the formation of spec ific cross dimers and trimers. Mechanistic studies on the selective trimeri zation of HC=CSiMe3 show that the first step in the catalytic cycle is the C=C bond insertion of the terminal alkyne into the actinide-acetylide bond. The kinetic rate law is first order in organoactinide and in alkyne, with Delta H-double dagger = 11.1(3) kcal mol(-1) and Delta S-double dagger = - 45.2(6) eu. The turnover-limiting step is the release of the organic oligom er from the alkenyl-actinide complex. The latter key organometallic interme diate has been characterized by spectroscopic and poisoning studies. A plau sible mechanistic scenario is proposed for the oligomerization of terminal alkynes.