Reactivity of Hydrogen Halide Adducts of Triosmium Clusters. 2. Synthesis of μ-η1- and μ-η1:η6-Phenyl Clusters

• Published in: Organometallics 1996-10, Vol.15 (21), p.4473-4479
• Main Authors: Kabir, Shariff E, Rosenberg, Edward, Stetson, Jeffrey, Yin, Mingzhi, Ciurash, Joana, Mnatsakanova, Karina, Hardcastle, Kenneth I, Noorani, Hosai, Movsesian, Naira
• Format: Article
• Language: English
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om960378z

The reaction of Os3(CO)9(μ-H)2(μ-η2-CN(CH2)3)Br (2) with diphenyl mercury yields the μ-η1-phenyl derivative Os3(CO)10(μ-η2-CN(CH2)3)(μ-η1-C6H5) (3). Compound 3 converts to the novel μ-η1:η6-phenyl derivative Os3(CO)8(μ-η2-CN(CH2)3)(μ-η1:η6-C6H5) (4) on thermolysis in octane. The solid-state structure of 4 is reported. In order to clear up ambiguities in the location of the hydrides for the previously reported 2, we report the solid-state structure and solution dynamics of Os3(CO)9(μ-H)2(μ-η2-CNCH(CH3)CH2CH2)Br (6), where carbon−nitrogen disordering is obviated by the presence of the 2-methyl group. The further reaction of 2 with excess HBr results in degradation of the cluster and the isolation of Os2(CO)6(μ-H)(μ-η2-CHNH(CH)3)Br2 (7). This compound represents an unusual example of acid-promoted hydrogenation of a carbon−nitrogen double bond and is an essential reversal of the dehydrogenation associated with the formation of the μ-imidoyl ligands in the title complexes.