Antimony(i) → Pd(ii) complexes with the (μ-Sb)Pd2 coordination framework

Abstract

The reaction of the antimony(I) compound ArSb (1) (where Ar = C₆H₃-2,6-(CHNtBu)₂) with various dimeric allyl palladium(II) complexes [Pd(η³-allyl)(μ-X)]₂ (where allyl = C₃H₅ or C₃H₄Me; X = Cl or CF₃CO₂) in a 1 : 1 stoichiometric ratio gave unique complexes with the μ-ArSb moiety bridging two palladium fragments, i.e. [{Pd(η³-C₃H₅)Cl}₂(μ-ArSb)] (2), [{Pd(η³-C₃H₄Me)Cl}₂(μ-ArSb)] (3) and [{Pd(η³-C₃H₅)(CF₃CO₂)}₂(μ-ArSb)] (4). Compound 1 serves formally as a 4e donor in 2–4. The treatment of 2 with another equivalent of ArSb led to the formation of the [Pd(η³-C₃H₅)(Cl)(μ-ArSb)] complex (5), proving that 1 is able to function as a 2e donor in target complexes as well. The structures of 2–5 were described in detail both in solution (NMR and mass spectrometry) and in the solid state (single crystal X-ray diffraction analysis). DFT methods were used to compare bonding in the 1 : 1 (5) and 1 : 2 (2) complexes. Furthermore, a comprehensive ¹²¹Sb Mössbauer spectroscopic investigation of complexes 2 and 5 along with parent ArSbCl₂ (6) and 1 was performed. For comparison, complexes [Fe(CO)₄(ArSb)] (7) and [Mo(CO)₅(ArSb)] (8) were also included in this study.