Synthesis and reactivity of new (methoxy)methyl complexes of manganese(I) and rhenium(I)

Eva Hevia, Daniel Miguel, Julio Perez, Victor Riera

Research output: Contribution to journalArticle

5 Citations (Scopus)

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)].

LanguageEnglish
Pages4909-4912
Number of pages4
JournalOrganometallics
Volume25
Issue number20
DOIs
Publication statusPublished - 25 Sep 2006

Fingerprint

Rhenium
Nucleophiles
Styrene
rhenium
Manganese
Nuclear magnetic resonance spectroscopy
manganese
Infrared spectroscopy
reactivity
X ray diffraction
nucleophiles
synthesis
styrenes
nuclear magnetic resonance
diffraction
spectroscopy
x rays
methyl triflate

Keywords

  • carbonyl-diimine complexes
  • ligands
  • alkenes
  • cyclopropanation
  • synthase

Cite this

Hevia, Eva ; Miguel, Daniel ; Perez, Julio ; Riera, Victor. / Synthesis and reactivity of new (methoxy)methyl complexes of manganese(I) and rhenium(I). In: Organometallics. 2006 ; Vol. 25, No. 20. pp. 4909-4912.
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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 journalArticle

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

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