Studies of ligand additions to coordinatively unsaturated dirhenium complexes containing the bulky PBu3t ligand

Richard D. Adams, Burjor Captain, Perry J. Pellechia

Research output: Contribution to journalArticle

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Abstract

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.

Original languageEnglish
Pages (from-to)6564-6575
Number of pages12
JournalOrganometallics
Volume26
Issue number26
DOIs
StatePublished - Dec 17 2007
Externally publishedYes

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Carbon Monoxide
Ligands
ligands
metals
atoms
marking
Metals
electrons
nitriles
Atoms
configurations
adducts
Labeling
Electrons
single crystals
diffraction
Nitriles
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Studies of ligand additions to coordinatively unsaturated dirhenium complexes containing the bulky PBu3t ligand. / Adams, Richard D.; Captain, Burjor; Pellechia, Perry J.

In: Organometallics, Vol. 26, No. 26, 17.12.2007, p. 6564-6575.

Research output: Contribution to journalArticle

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title = "Studies of ligand additions to coordinatively unsaturated dirhenium complexes containing the bulky PBu3t ligand",
abstract = "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.",
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N2 - 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.

AB - 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.

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