Reactions of the multiply bonded dirhenium complexes [Re2X4(L–L)2]n+(X = Cl or Br, L–L = Ph2PCH2CH2PPh2 or Ph2PCH2CH2AsPh2; n= 0 or 1) with isocyanides and nitriles. Reaction without metal–metal bond disruption

Abstract

The reaction of paramagnetic [Re₂X₄(L–L)₂] PF₆ with RNC (X = CI or Br, L–L = Ph₂PCH₂CH₂PPh₂ or Ph₂PCH₂CH₂AsPh₂, R = Prⁱ or Bu^t) proceeds with reduction of the dirhenium core to yield the diamagnetic complexes [Re₂X₃(L–L)₂(CNR)] PF₆. These isocyanide-containing compounds can be oxidized to the paramagnetic dications using NOPF₆ as the oxidant. The reactions of complexes [Re₂X₄(L–L)₂] PF₆ with nitriles RCN (R = Me or Et) in the presence of TIPF₆ yield the paramagnetic complexes [Re₂X₃(L–L)₂(NCR)][PF₆]₂, which can be reduced to the corresponding monocations using LiBEt₃H or cobaltocene as the reductants. The staggered rotational geometry of the parent complexes [Re₂X₄(L–L)₂]ⁿ⁺(n= 0 or 1) is believed to be retained in [Re₂X₃(L–L)₂(CNR)]ⁿ⁺ and [Re₂X₃(L-L)₂(NCR)]ⁿ⁺(n= 1 or 2).