Reactions of Ru3(CO)10(NCMe)2 with ethyne: molecular structures of some prototypical cluster complexes

Abstract

Formation of Ru₄, Ru₅ and Ru₆ complexes accompanies the synthesis of the previously described of Ru₃(µ₃-C₂H₂)(µ-CO)(CO)₉ 1 [from Ru₃(CO)₁₀(NCMe)₂ and C₂H₂] and its conversion to Ru₃(µ-H)(µ₃-C₂H)(CO)₉ 2. In Ru₄(µ₄-C₂H₂)(CO)₁₂ 4, the ethyne forms part of the pseudo-octahedral C₂Ru₄. In contrast, µ₄-η²-CCH₂ ligands are found in Ru₅(µ₄-CCH₂)(CO)₁₅ 5 and Ru₆(µ₄-CCH₂)₂(CO)₁₆ 7; in the former, the Ru₅ core is an edge-bridged tetrahedron, while in 7, two butterflies share an RuRu double bond [2.686(1) Å]. Other minor products are Ru₅(µ-CHCHCCH₂)(CO)₁₅ 6 and Ru₆(µ-H)(µ₄-C)(µ-CCMe)(µ-CO)(CO)₁₆ 8. Crystal structures of 1, 2, 4, 5 and 7·CH₂Cl₂ are reported.