The reaction of [Os 3(CO) 10(CH 3CN) 2] with carboxylic acids: the crystal and molecular structures of [Os 3H(CO) 10(C 6H 4(OH)CO 2)] and [Os 3H(CO) 10(C 6H 5COS)]

• Published in: Journal of organometallic chemistry Vol. 556; no. 1; pp. 197 - 205
• Main Authors: Ainscough, Eric W, Brodie, Andrew M, Coll, Richard K, Coombridge, Brett A, Waters, Joyce M
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.04.1998
• Subjects: Carboxylate; Crystal structure; Osmium cluster; Thiocarboxylate; Osmium cluster; Carboxylate; Thiocarboxylate; Crystal structure
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(97)00772-9

The triosmium cluster, [Os 3(CO) 10(CH 3CN) 2], undergoes reaction with carboxylic acids to form clusters containing a chelating μ, η 2-carboxylate ligand and a hydride bridge across one edge of the triangle via an intermediate species postulated, from IR and NMR studies, to contain a coordinated μ, η 1-carboxylate ion. The structure of the cluster, [Os 3H(CO) 10(C 6H 4(OH)CO 2)] ( 1), has been determined by single-crystal X-ray diffraction and contains the 2-hydroxobenzoate ligand bound via the carboxylate oxygens in the μ, η 2-mode. A thiocarboxylate analogue of the postulated intermediate, viz. [Os 3H(CO) 10(C 6H 5COS)] ( 2), has been obtained and its structure determined by single crystal X-ray diffraction. The C 6H 5COS − ion, which is bound in the μ, η 1-mode through the sulfur atom, bridges two of the osmium atoms of the triangle.