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 E.
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 -