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Reactions of Tp–Os nitrido complexes with the nucleophiles hydroxide and thiosulfate

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Title: Reactions of Tp–Os nitrido complexes with the nucleophiles hydroxide and thiosulfate
Authors: Wu, Adam1, Dehestani, Ahmad1, Saganic, Erik1, Crevier, Thomas J.1, Kaminsky, Werner, Cohen, Dawn E., Mayer, James M. mayer@chem.washington.edu
Source: Inorganica Chimica Acta. Jun2006, Vol. 359 Issue 9, p2842-2849. 8p.
Subjects: Carbon, Optical diffraction, Platinum group, Optics
Abstract: Abstract: The reaction between TpOs(N)Cl2 (1) [Tp=hydrotris(1-pyrazolyl)borate] and aqueous ( n Bu4N)(OH) in THF-d 8 forms the nitrosyl complex TpOs(NO)Cl2 (5) among other products, suggesting an initial hydroxide attack at the nitrido ligand. In contrast, the reaction of the acetate complex TpOs(N)(OAc)2 (2) with NaOH in Me2CO/H2O yields the osmium bis-hydroxide complex TpOs(N)(OH)2 (3), which has been structurally characterized by single-crystal X-ray diffraction. Acetate for hydroxide exchange could occur by ligand substitution or by nucleophilic attack at the carbonyl carbon of the acetate ligands (saponification). Reacting 2 with Na18OH in H2 18O/CD3CN yields predominantly doubly 18O-labeled TpOs(N)(18OH)2 (3- 18 O 2 ) and unlabeled acetate, by ESI/MS and 13C{1H} NMR. This indicates that hydroxide reacts by substitution rather than by attack at the ligand. The reaction of 2 with the softer nucleophile thiosulfate occurs at the nitrido ligand, giving the thionitrosyl complex TpOs(NS)(OAc)2 (4). Reacting 4 with NaOH in (CD3)2CO/D2O also generates the bis-hydroxide complex 3. [Copyright &y& Elsevier]
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Abstract:Abstract: The reaction between TpOs(N)Cl2 (1) [Tp=hydrotris(1-pyrazolyl)borate] and aqueous ( n Bu4N)(OH) in THF-d 8 forms the nitrosyl complex TpOs(NO)Cl2 (5) among other products, suggesting an initial hydroxide attack at the nitrido ligand. In contrast, the reaction of the acetate complex TpOs(N)(OAc)2 (2) with NaOH in Me2CO/H2O yields the osmium bis-hydroxide complex TpOs(N)(OH)2 (3), which has been structurally characterized by single-crystal X-ray diffraction. Acetate for hydroxide exchange could occur by ligand substitution or by nucleophilic attack at the carbonyl carbon of the acetate ligands (saponification). Reacting 2 with Na18OH in H2 18O/CD3CN yields predominantly doubly 18O-labeled TpOs(N)(18OH)2 (3- 18 O 2 ) and unlabeled acetate, by ESI/MS and 13C{1H} NMR. This indicates that hydroxide reacts by substitution rather than by attack at the ligand. The reaction of 2 with the softer nucleophile thiosulfate occurs at the nitrido ligand, giving the thionitrosyl complex TpOs(NS)(OAc)2 (4). Reacting 4 with NaOH in (CD3)2CO/D2O also generates the bis-hydroxide complex 3. [Copyright &y& Elsevier]
ISSN:00201693
DOI:10.1016/j.ica.2005.11.033