Abstract
The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) with ClCH2OCH3 afford the (methoxy) methyl complexes [M(CH2OCH3)(CO)(3)(bipy)] (M = Mn, 1; Re, 2), characterized by IR and NMR spectroscopy and, in the case of 1, also by X-ray diffraction. Highly electrophilic species, presumably cationic alkylideneoxonium complexes, although they were not detected, were prepared in situ by reaction of 1 and 2 with methyl triflate. These species react with neutral nucleophiles such as SMePh to generate the alkylidenesulfonium complexes [M(CH2SPhMe)-(CO)(3)(bipy)](+)[OTf](-) (M = Mn, 3; Re, 4) and with styrene to give phenylcyclopropane and the corresponding triflate complexes [M(OTf)(CO)(3)(bipy)].
| Language | English |
|---|---|
| Pages | 4909-4912 |
| Number of pages | 4 |
| Journal | Organometallics |
| Volume | 25 |
| Issue number | 20 |
| DOIs | |
| Publication status | Published - 25 Sep 2006 |
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Keywords
- carbonyl-diimine complexes
- ligands
- alkenes
- cyclopropanation
- synthase
Cite this
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Synthesis and reactivity of new (methoxy)methyl complexes of manganese(I) and rhenium(I). / Hevia, Eva; Miguel, Daniel; Perez, Julio; Riera, Victor.
In: Organometallics, Vol. 25, No. 20, 25.09.2006, p. 4909-4912.Research output: Contribution to journal › Article
TY - JOUR
T1 - Synthesis and reactivity of new (methoxy)methyl complexes of manganese(I) and rhenium(I)
AU - Hevia, Eva
AU - Miguel, Daniel
AU - Perez, Julio
AU - Riera, Victor
PY - 2006/9/25
Y1 - 2006/9/25
N2 - The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) with ClCH2OCH3 afford the (methoxy) methyl complexes [M(CH2OCH3)(CO)(3)(bipy)] (M = Mn, 1; Re, 2), characterized by IR and NMR spectroscopy and, in the case of 1, also by X-ray diffraction. Highly electrophilic species, presumably cationic alkylideneoxonium complexes, although they were not detected, were prepared in situ by reaction of 1 and 2 with methyl triflate. These species react with neutral nucleophiles such as SMePh to generate the alkylidenesulfonium complexes [M(CH2SPhMe)-(CO)(3)(bipy)](+)[OTf](-) (M = Mn, 3; Re, 4) and with styrene to give phenylcyclopropane and the corresponding triflate complexes [M(OTf)(CO)(3)(bipy)].
AB - The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) with ClCH2OCH3 afford the (methoxy) methyl complexes [M(CH2OCH3)(CO)(3)(bipy)] (M = Mn, 1; Re, 2), characterized by IR and NMR spectroscopy and, in the case of 1, also by X-ray diffraction. Highly electrophilic species, presumably cationic alkylideneoxonium complexes, although they were not detected, were prepared in situ by reaction of 1 and 2 with methyl triflate. These species react with neutral nucleophiles such as SMePh to generate the alkylidenesulfonium complexes [M(CH2SPhMe)-(CO)(3)(bipy)](+)[OTf](-) (M = Mn, 3; Re, 4) and with styrene to give phenylcyclopropane and the corresponding triflate complexes [M(OTf)(CO)(3)(bipy)].
KW - carbonyl-diimine complexes
KW - ligands
KW - alkenes
KW - cyclopropanation
KW - synthase
U2 - 10.1021/om060459n
DO - 10.1021/om060459n
M3 - Article
VL - 25
SP - 4909
EP - 4912
JO - Organometallics
T2 - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 20
ER -