Rhodium(II) Acetate Donor–Acceptor Complexes Rh2(OAc)4(Diox)2, Rh2(OAc)4(Dmso)2, and Rh2(OAc)4[(4-FC6H4)3Sb]2: Synthesis and Structure

Abstract

The rhodium diacetate complexes with dioxane Rh₂(OAc)₄(Diox)₂ (I) and dimethyl sulfoxide Rh₂(OAc)₄(Dmso)₂ (II) have been synthesized by dissolving rhodium diacetate [Rh₂(OAc)₄] in dioxane (Diox) and dimethyl sulfoxide (Dmso) with the further slow evaporation of the solvent. Rh₂(OAc)₄[(4-FC₆H₄)₃Sb]₂ (III) has been synthesized by the reaction between [Rh₂(OAc)₄] and tris-4-fluorophenylantimony in acetonitrile. Using X-ray diffraction, it has been established that the rhodium atoms in complexes I–III have a slightly distorted octahedral coordination: the angles ORhRh, ORhO, 176.56(6)°–177.72(4)° (I); SRhRh, ORhO, 174.79(9)°–179.271(13)° (II); SbRhRh, ORhO 173.590(19)°–175.48(10)° (III); bonds Rh–Rh, Rh–O_Ac, Rh–O_Diox, 2.380(3), 2.037(3)–2.046(3), 2.335(3) Å (I); Rh–Rh, Rh–O, Rh–S, 2.4288(10), 2.034(3)–2.046(3), 2.7258(10) Å (II); Rh–Rh, Rh–O, Rh–Sb, 2.4183(12), 2.033(3)–2.044(3), 2.7113(13)–2.7120(13) Å (III). The structural organization in crystals of complexes I–III is caused by weak hydrogen bonds Н···O_Diox (2.50–2.72 Å), Н···O_Ac (2.57 Å) (I), Н···O_Dmso 2.48–2.71 Å, Н···O_Ac 2.65, 2.66 Å (II) H···F (2.56–2.62 Å), and H···O (2.68–2.71 Å) (III).