Abstract
The formation of thorium metallacyclopentadiene and metallacyclopropene complexes is significantly influenced by the steric and electronic properties of the internal alkyne employed during their syntheses. The reduction of (η5-C5Me5)2ThCl2 (2) with potassium graphite (KC8) or lithium in the presence of internal phenyl(alkyl)acetylenes (PhC≡CR) selectively yields the corresponding Cs-symmetric thorium metallacyclopentadienes (η5-C5Me5)2Th[η2-C(Ph)═C(R)C(Ph)═C(R)] (R = Me (4), iPr (5), C6H11 (6)), while the phenyl(silyl)acetylene PhC≡CSiHMe2 gives the C2v-symmetric metallacyclopentadiene (η5-C5Me5)2Th[η2-C(SiHMe2)═C(Ph)C(Ph)═C(SiHMe2)] (7). However, the sterically more encumbered acetylene derivative PhC≡CSiMe3 affords the chloro metallacyclopropene complex [(η5-C5Me5)2Th(η2-C2Ph(SiMe3))(Cl)][Li(EDM)2] (8), whereas Me3SiC≡CSiMe3 forms the chloro alkenyl complex [(η5-C5Me5)2Th[C(SiMe3)═CHSiMe3](Cl) (9), in which the chloro metallacyclopropene intermolecularly activates a C–H bond of the solvent (C7H8). Densi...
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