Synthesis of mononuclear, dinuctear and oligomeric rigid-rod acetylide complexes of rhodium, and the molecular structure of [Rh(PMe3)4(CC–p-C6H4–CC)Rh(PMe3)4]

Abstract
Reaction of two equivalents of [Rh(PMe3)4]Cl with HCC–X–CCH (X = none, p-C6H4, p-C6F4, p-C6H4-C6H4-p) yields the dinuclear acetylide bridged dications cis-cis-[Rh(PMe3)4(H)(CC–X–CC)Rh(PMe3)4(H)]2+[ Cl]2, whereas reaction of [Rh(PMe3)4(Me)] with HCC–X–CCH (X =p-C6H4, p-C6H4–C6H4-p) yields neutral mononuclear, dinuclear or oligomeric rigid-rod complex mer-trans-[Rh(PMe3)3(H)(CC–X–CCH)2], [Rh(PMe3)4(CC–X–CC)Rh(PMe3)4] or mer-trans-[–Rh(PMe3)3(H)–CC–X–CC–]n, depending upon the stoichiometry employed (1 : 2, 2 :1, or 1 :1 respectively); the crystal and molecular structure of the dinuclear RhI complex [Rh(PMe3)4(CC–C6H4–CC)Rh(PMe3)4] has been determined by X-ray diffraction, and soluble rigid-rod oligomers have been isolated from reactions employing the PBun 3 ligand.

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