Abstract
The reaction of [(Cp'''Co)(2)(mu, eta(2:2)-As-2)(2)] with the decamethylsamarocenes [Cp*Sm-2(THF)(2)] or [Cp*Sm-2], or the bis(tetramethyl-n-propyl) samarocene [(C5Me4(n-propyl))(2)Sm] resulted in the mixed d/f polyarsenides [(Cp'''Co)(2)As4Sm(h(5)C(5)Me(4)R) (2)] (R=Me, n-propyl). They are the first structural representatives of open chain- like polyarsenides as ligands in the coordination ...
Abstract
The reaction of [(Cp'''Co)(2)(mu, eta(2:2)-As-2)(2)] with the decamethylsamarocenes [Cp*Sm-2(THF)(2)] or [Cp*Sm-2], or the bis(tetramethyl-n-propyl) samarocene [(C5Me4(n-propyl))(2)Sm] resulted in the mixed d/f polyarsenides [(Cp'''Co)(2)As4Sm(h(5)C(5)Me(4)R) (2)] (R=Me, n-propyl). They are the first structural representatives of open chain- like polyarsenides as ligands in the coordination sphere of lanthanides. Their formation can be explained by an intramolecular As-As coupling within the cobalt polyarsenide complex after reduction by the divalent samarium complex. Density functional theory calculations give insight into the structural change of the (As-2)(2) unit in [{Cp'''Co(mu, eta(2:2)-As-2)}(2)] upon reduction.
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