Stepwise Construction of Polynuclear Complexes of Rhodium and Iridium Assisted by Benzimidazole-2-thiol. NMR and X-ray Diffraction Studies.
Reactions of [M(2)(&mgr;-Cl)(2)(cod)(2)] (cod = 1,5-cyclooctadiene, M = Rh, Ir) with benzimidazole-2-thiol (H(2)Bzimt) afford the mononuclear complexes [MCl(H(2)Bzimt)(cod)] (M = Rh (1), Ir (2)) for which a S-coordination of the ligand is proposed based on their spectroscopic data. The dinuclear complexes [M(2)(&mgr;-HBzimt)(2)(cod)(2)] (M = Rh (3), Ir (4)) are isolated from the reaction of [M(acac)(cod)] and benzimidazole-2-thiol. They contain the monodeprotonated ligand (HBzimt(-)) bridging the two metals in a &mgr;(2)-(1kappaN,2kappaS) coordination mode and in a relative cis,cis-HT arrangement. Complexes 3 and 4 react with the appropriate species [M(cod)(Me(2)CO)(2)](+) to afford the trinuclear cationic aggregates [M(3)(&mgr;-HBzimt)(2)(cod)(3)](+) (M = Rh (5), Ir (6)) and with the [M'(2)(&mgr;-OMe)(2)(cod)(2)] compounds to give the homo- and heterotetranuclear complexes [MM'(&mgr;-Bzimt)(cod)(2)](2) (M = M' = Rh (7), Ir (8); M = Ir, M' = Rh (9)) containing the dideprotonated ligand (Bzimt(2)(-)). The trinuclear neutral complexes [M(3)(&mgr;-Bzimt)(&mgr;-HBzimt)(cod)(3)] are intermediates detected in the synthesis of the tetranuclear complexes. Protonation of 9 with HBF(4) gives the unsymmetrical complex [Ir(2)Rh(&mgr;-HBzimt)(2)(cod)(3)]BF(4) (10). This reaction involves the protonation of the bridging ligands followed by the removal of one "Rh(cod)" moiety to give a single isomer. The molecular structure of [Rh(2)(&mgr;-Bzimt)(cod)(2)](2) (7) has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P2(1)/n, a = 20.173(5) Å, b = 42.076(8) Å, c = 10.983(3) Å, beta = 93.32(2) degrees, Z = 8, 7145 reflections, R = 0.0622, and R(w) = 0.0779. The complete assignment of the resonances of the (1)H NMR spectra of the complexes 3, 4, and 7-9 was carried out by selective decoupling, NOE, and H,H-COSY experiments. The differences in the chemical shifts of the olefinic protons are discussed on the basis of steric and magnetic anisotropy effects.
Tejel
Cristina
C
Departamento de Química Inorgánica, ICMA, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain, and Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Centro di Studio per la Structturistica Diffrattometrica del CNR, Università di Parma, Viale delle Scienze 78, I-43100 Parma, Italy.
Villarroya
B. Eva
BE
Ciriano
Miguel A.
MA
Oro
Luis A.
LA
Lanfranchi
Maurizio
M
Tiripicchio
Antonio
A
Tiripicchio-Camellini
Marisa
M