Structures and Properties of 4-phpy, pyz, and 4,4′-bpy Adducts of Lantern-Type Dirhodium Complexes with µ-Formamidinato and µ-Carboxylato Bridges

Abstract

Dinuclear and polymer complexes of 4-phenylpyridine (4-phpy), pyazine (pyz), and 4,4′-bipyridine (4,4′-bpy) were prepared by using cis-[Rh2(4-Me-pf)2(O2CR)2] (4-Me-pf- =N,N’-bis(4-methylphenyl)formamidinate anion; R = CF3 and CMe3) as precursor dinuclear units. The dinuclear structures of cis-[Rh2II,II(4-Me-pf)2(O2CR)2(4-phpy)2] and cis-[Rh2II,III(4-Me-pf)2(O2CCMe3)2(4-phpy)2]BF4 and polymer structures of [Rh2II,II(4-Me-pf)2(O2CR)2(L)]n (L = pyz and 4,4′-bpy) were confirmed by X-ray crystal structure analyses. In these complexes, the lantern-type dinuclear core structures with cis-(2:2) arrangement of formamidinato (4-Me-pf-) and carboxylato ligands are preserved with Rh–Rh distances of 2.44–2.47 Å, regardless of the difference in the axial ligand and oxidation state Rh2II,II or Rh2II,III. In the cyclic voltammograms (CVs) in CH2Cl2, the redox potentials for Rh2II,III/Rh2II,II were estimated as E1/2 = 0.07 V and −0.28 V (vs. Fc+/Fc) for cis-[Rh2(4-Me-pf)2(O2CCF3)2(4-phpy)2] and cis-[Rh2(4-Me-pf)2(O2CCMe3)2(4-phpy)2], respectively, negatively shifted by 0.16 and 0.12 V compared with those of corresponding parent dinuclear complexes. The results were interpreted that the axial interaction with 4-phpy ligands makes the Rh2II,II core oxidized easily. The oxidized complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2(4-phpy)2]BF4 is paramagnetic, which was confirmed by effective magnetic moment value μeff = 1.90 μB at 300 K per Rh2II,III unit (S = 1/2). The polymer complexes [Rh2(4-Me-pf)2(O2CR)2(L)]n (L = pyz and 4,4′-bpy) showed Type II gas-adsorption properties for N2.