Cyclodiphosphazane cis‐{(o‐MeOC6H4O)P(μ‐NtBu)}2 as a Bridging Bidentate Ligand: Synthesis, Structures of Heterometallic Complexes, and Halogen Exchange Between Rh–Cl and Cu–X (X = Br, I)

摘要: The mononuclear rhodium complexes of cyclodiphosphazane [(cod)RhCl{L-κP}] (1a) (L = cis-{(o-MeOC6H4O)P(μ-NtBu)}2) and trans-[Rh(CO)Cl{L-κP}2] (1b) react in a 1:1 molar ratio with [AuCl(SMe2)] to form the heteronuclear [(cod)RhCl{μ-L-κP,κP}AuCl] (2) trans-[Rh(CO)Cl{μ-L-κP,κP}2(AuCl)2] (7), respectively, quantitative yield. reaction between 1a CuCl afforded tetranuclear complex [(cod)RhCl{μ-L-κP,κP}Cu(μ-Cl)]2 (3). Under similar conditions 1 reacts 2 equiv. CuX (X Br, I) produce [(cod)RhBr{μ-L-κP,κP}Cu(μ-Br)]2 (4) [((cod)RhI{μ-L-κP,κP})2Cu(μ-X)2Cu] ≈ mixture Cl I disordered over both sites) (5), which two molecules are bridged by rhombic, disordered, mixed halide [Cu(μ-X)2Cu] (5: X Br; 6: Cl, unit. crystal structures 4 5 confirm halogen exchange Rh–Cl moieties leads formation Rh–Br Rh–I bonds. heterodinuclear RhI/PdII [(cod)RhCl{μ-L-κP,κP}PdCl(η3-C3H5)] (6) was synthesized [PdCl(η3-C3H5)]2 2:1 ratio. Reaction 1b CuI [Rh(CO)I{μ-L-κP,κP}2Cu(μ-I)]2 (8) containing terminal uncoordinated phosphorus(III) centers irrespective reactant conditions. Halogen bond also observed during preparation 8. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)