Five new complexes were obtained from the reaction of Re 3(CO)12(μ-H)3 with PBu3 t. These are Re2(CO)8(μ-PBu2 t)(μ-H), 1, Re2(CO)7(μ-PBu 2t)(PBu2tH)(μ-H), 2, HRe(CO) 4(PBu3t), 3, Re2(CO) 6(PBu3t)(μ-PBu2 t)(μ-H), 4, and Re2(CO)5(PBu 3t)(PBu2tH)(μ-PBu 2tO)(μ-H), 5. Compounds 4 and 5 are electronically unsaturated by the amount of two electrons; namely, one of the metal atoms has an 18-electron configuration and the other metal atom has a 16-electron configuration. Compound 4 adds CO and the nitriles MeCN and PhCN, reversibly, to form the electronically saturated 1:1 adducts Re2(CO) 7(PBu3t)(μ-PBu2 t)(μ-H), 6, Re2(CO)6(NCMe)(PBu 3t)(μ-PBu2t)(μ-H), 7, and Re2(CO)6(NCPh)(PBu3t)(μ-PB 2t)(μ-H), 8, respectively. 13CO labeling studies have shown that the CO ligand that is added to 4 to form 6 is added at the electronically saturated metal atom and one of the originally coordinated CO ligands is shifted to the unsaturated metal atom. Compound 5 also adds 1 equiv of CO to form the complex Re2(CO)6(PBu3 t)(PBu2tH)(μ-PBu2 tO)(μ-H), 9.13CO labeling studies have shown that the added CO ligand was added to the unsaturated metal atom in this case. All of the new compounds were characterized structurally by single-crystal X-ray diffraction analyses.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry