Reactivity of triosmium clusters with 3,4-dimethyl-1-phenylphosphole and cyanoethyldi-tert-butylphosphine ligands: X-ray crystal structures of [Os^sub 3^(CO)^sub 9^([mu]-OH)([mu]-H)([eta]^sup 1^-PhPC^sub 4^H2Me^sub 2^)] and [Os^sub 3^(CO)^sub 11^([eta]^sup 1^-^sup t^Bu^sub 2^PC^sub 2^H^sub 4^CN)]

• Published in: Transition metal chemistry (Weinheim) 2014-03, Vol.39 (2), p.239
• Main Authors: Otero, Yomaira, Peña, Deisy, De Sanctis, Ysaura, Arce, Alejandro, Ocando-mavarez, Edgar, Machado, Rubén, Gonzalez, Teresa
• Format: Article
• Language: English
• ISSN: 0340-4285; 1572-901X
• DOI: 10.1007/s11243-013-9796-3

Reaction of [Os^sub 3^([mu]-H)^sub 2^(CO)^sub 10^] with 3,4-dimethyl-1-phenylphosphole in refluxing cyclohexane affords two substituted triosmium clusters: [Os^sub 3^(CO)^sub 9^([mu]-H)([mu]^sup 3^:η^sup 1^:η^sup 1^:η^sup 2^-PhPC^sub 4^H^sub 3^Me^sub 2^)] (1) and [Os^sub 3^(CO)^sub 9^(H)([mu]^sup 2^-η^sup 1^:η^sup 2^-PhPC^sub 4^H^sub 4^Me^sub 2^)] (2), of which cluster 2 exhibits two chromatographically non-separable isomeric forms attributed to terminal and bridging coordination of the hydride ligand, respectively. When this reaction is performed in refluxing THF, the only product is the cluster [Os^sub 3^(CO)^sub 9^([mu]-OH)([mu]-H)(η^sup 1^-PhPC^sub 4^H2Me^sub 2^)] (3). Crystallographic information obtained for cluster 3 shows the phosphole ligand occupying an equatorial position, as expected, while the OH group is asymmetrically bridging unlike previously reported similar compounds. Additionally, interaction of the labile cluster [Os^sub 3^(CO)^sub 11^(CH^sub 3^CN)] with cyanoethyldi-tert-butylphosphine in dichloromethane at room temperature was found to give [Os^sub 3^(CO)^sub 11^(η^sup 1^-^sup t^Bu^sub 2^PC^sub 2^H^sub 4^CN)] (4) as the only product; its crystallographic characterization shows that the phosphine ligand coordinates by means of the phosphorus atom in an equatorial fashion, analogous to compound 3.[PUBLICATION ABSTRACT]