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Preparation and characterization of novel os−diolefin dimers: New entry to os−cyclooctadiene complexes

AutorEsteruelas, Miguel A. ; García-Yebra, Cristina ; Oliván, Montserrat ; Oñate, Enrique
Fecha de publicaciónnov-2006
EditorAmerican Chemical Society
CitaciónInorganic Chemistry 45(25): 10162-10171 (2006)
ResumenThe complex [H(EtOH)2][{OsCl(è4-COD)}2(í-H)(í-Cl)2] (1) has been prepared in high yield by treatment of OsCl3â 3H2O (54% Os) with 1,5-cyclooctadiene in ethanol under reflux. Under air, it is unstable and undergoes oxidation by action of O2 to afford the neutral derivative {OsCl(è4-COD)}2(í-H)(í-Cl)2 (2). The terminal chlorine ligands of the anion of 1 are activated toward nucleophilic substitution. Thus, reaction of the salt [NBu4][{OsCl(è4-COD)}2- (í-H)(í-Cl)2] (1a) with NaCp in toluene gives [NBu4][{Os(è1-C5H5)(è4-COD)}(í-H)(í-Cl)2{OsCl(è4-COD)}] (3) as a result of the replacement of one of the terminal chlorine atoms by the cyclopentadienyl ligand. The CH2 group of the latter can be deprotonated by the bridging methoxy ligand of the iridium dimer [Ir(í-OMe)(è4-COD)]2. The reaction leads to the trinuclear derivative [NBu4][{(è4-COD)Ir(è5-C5H4-è1)Os(è4-COD)}(í-H)(í-Cl)2{OsCl(è4-COD)}] (4) containing a bridging C5H4 ligand that is è1-coordinated to an osmium atom of the dimeric unit and è5-coordinated to the Ir(è4-COD) moiety. Salt 1a also reacts with LiCtCPh. In this case, the reaction produces the substitution of both terminal chlorine ligands to afford the bis(alkynyl) derivative [NBu4][{Os(CtCPh)(è4-COD)}2(í-H)(í-Cl)2] (5). Complexes 1, 2, 3, and 4 have been characterized by X-ray diffraction analysis. Although the separations between the osmium atoms are short, between 2.6696(4) and 2.8633(5) Å, theoretical calculations indicate that only in 2 is there direct metal-metal interaction, as the bond order is 0.5.
Descripción10 pages, 1 table, 8 figures, 1 scheme.-- Supporting Information Available: http://pubs.acs.org.
Versión del editorhttp://dx.doi.org/10.1021/ic0612799
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