Abstract
This combined experimental and computational study demonstrates how a metal center can drastically influence the reactivity of a coordinated ligand. We found that the consecutive formation of zerovalent bimetallic complexes proceeds by fast n2-C - C coordination of only one Pd(PEt3)2 moiety, which then significantly slows down the subsequent reaction. Electronic effects induced by complexation of the first metal center have a major effect on the subsequent formation of the bimetallic complexes. These effects are reduced by partial fluorination of the bis(vinylpyridine)-arene ligand. The monometallic complexes display migration of the Pd(PEt3)2 moiety between the two olefinic bonds of the corresponding ligand, as indicated by various solution NMR experiments, including variable-temperature NMR spectroscopy, 2D 1H-1H exchange spectroscopy, and spin saturation transfer. Density functional theory studies were performed at the SMD(toluene)-PBE0+d(v3)/B2//B97D/B1 level of theory.
| Original language | English |
|---|---|
| Pages (from-to) | 1098-1106 |
| Number of pages | 9 |
| Journal | Organometallics |
| Volume | 34 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Mar 23 2015 |
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ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Generation of MoNo- and bimetallic palladium complexes and mechanistic insight into an operative metal ring-walking process. / Orbach, Meital; Shankar, Sreejith; Zenkina, Olena V.; Milko, Petr; Diskin-Posner, Yael; van der Boom, Milko.
In: Organometallics, Vol. 34, No. 6, 23.03.2015, p. 1098-1106.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Generation of MoNo- and bimetallic palladium complexes and mechanistic insight into an operative metal ring-walking process
AU - Orbach, Meital
AU - Shankar, Sreejith
AU - Zenkina, Olena V.
AU - Milko, Petr
AU - Diskin-Posner, Yael
AU - van der Boom, Milko
PY - 2015/3/23
Y1 - 2015/3/23
N2 - This combined experimental and computational study demonstrates how a metal center can drastically influence the reactivity of a coordinated ligand. We found that the consecutive formation of zerovalent bimetallic complexes proceeds by fast n2-C - C coordination of only one Pd(PEt3)2 moiety, which then significantly slows down the subsequent reaction. Electronic effects induced by complexation of the first metal center have a major effect on the subsequent formation of the bimetallic complexes. These effects are reduced by partial fluorination of the bis(vinylpyridine)-arene ligand. The monometallic complexes display migration of the Pd(PEt3)2 moiety between the two olefinic bonds of the corresponding ligand, as indicated by various solution NMR experiments, including variable-temperature NMR spectroscopy, 2D 1H-1H exchange spectroscopy, and spin saturation transfer. Density functional theory studies were performed at the SMD(toluene)-PBE0+d(v3)/B2//B97D/B1 level of theory.
AB - This combined experimental and computational study demonstrates how a metal center can drastically influence the reactivity of a coordinated ligand. We found that the consecutive formation of zerovalent bimetallic complexes proceeds by fast n2-C - C coordination of only one Pd(PEt3)2 moiety, which then significantly slows down the subsequent reaction. Electronic effects induced by complexation of the first metal center have a major effect on the subsequent formation of the bimetallic complexes. These effects are reduced by partial fluorination of the bis(vinylpyridine)-arene ligand. The monometallic complexes display migration of the Pd(PEt3)2 moiety between the two olefinic bonds of the corresponding ligand, as indicated by various solution NMR experiments, including variable-temperature NMR spectroscopy, 2D 1H-1H exchange spectroscopy, and spin saturation transfer. Density functional theory studies were performed at the SMD(toluene)-PBE0+d(v3)/B2//B97D/B1 level of theory.
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U2 - 10.1021/acs.organomet.5b00051
DO - 10.1021/acs.organomet.5b00051
M3 - Article
AN - SCOPUS:84925423617
VL - 34
SP - 1098
EP - 1106
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 6
ER -