A General Pathway to Heterobimetallic Triple-Decker Complexes.

ABSTRACT: A systematic study on the reactivity of the triple-decker complex [(Cp'''Co)2 (?,?4 :?4 -C7 H8 )] (A) (Cp'''=1,2,4-tritertbutyl-cyclopentadienyl) towards sandwich complexes containing cyclo-P3 , cyclo-P4 , and cyclo-P5 ligands under mild conditions is presented. The heterobimetallic triple-decker sandwich complexes [(Cp*Fe)(Cp'''Co)(?,?5 :?4 -P5 )] (1) and [(Cp'''Co)(Cp'''Ni)(?,?3 :?3 -P3 )] (3) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)5 } fragments, leading to the complexes [(Cp*Fe)(Cp'''Co)(?3 ,?5 :?4 :?1 -P5 ){W(CO)5 }] (2?a), [(Cp*Fe)(Cp'''Co)(?4 ,?5 :?4 :?1 :?1 -P5 ){(W(CO)5 )2 }] (2?b), and [(Cp'''Co)(Cp'''Ni)(?3 ,?3 :?2 :?1 -P3 ){W(CO)5 }] (4), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp'''Ni)2 (?,?2 :?2 -P2 )] (5). All compounds were fully characterized using single-crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis.

SUBMITTER: Piesch M 

PROVIDER: S-EPMC7028134 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature