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 language | English |
|---|---|
| Pages (from-to) | 6564-6575 |
| Number of pages | 12 |
| Journal | Organometallics |
| Volume | 26 |
| Issue number | 26 |
| DOIs | |
| State | Published - Dec 17 2007 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
T1 - Studies of ligand additions to coordinatively unsaturated dirhenium complexes containing the bulky PBu3t ligand
AU - Adams, Richard D.
AU - Captain, Burjor
AU - Pellechia, Perry J.
PY - 2007/12/17
Y1 - 2007/12/17
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.
UR - http://www.scopus.com/inward/record.url?scp=38049125990&partnerID=8YFLogxK
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U2 - 10.1021/om700790c
DO - 10.1021/om700790c
M3 - Article
AN - SCOPUS:38049125990
VL - 26
SP - 6564
EP - 6575
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 26
ER -