Abstract
The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) compounds with ClCH2SR (R = Me, Ph) afford the (alkylthio)alkyl complexes [Mn(CH2SMe)(CO)(3)(bipy)] (1a), [Mn(CH2SPh)(CO)(3)-(bipy)] (1b), [Re(CH2SMe)(CO)(3)(bipy)] (2a), and [Re(CH2SMe)(CO)(3)(bipy)] (2b). Methylation at sulfur of these compounds with methyl triflate affords the methylidenesulfonium cations [Mn(CH2SMe2)(CO)(3)(bipy)](+) (5a), [Mn(CH2SMePh)(CO)(3)(bipy)](+) (5b), [Re(CH2SMe2)(CO)(3)(bipy)](+) (6a), and [Re(CH2SMePh)(CO)(3)(bipy)](+) (6b) as their triflate salts. These new compounds were characterized by IR and NMR spectroscopy, and the crystal structures of 1b, 2a, 5b, and 6b have been determined by X-ray diffraction. The sulfonium complexes are unreactive toward PPh3 and pyridine. The reactions of 5b and 6b with I-, PPh2-, and SEt(-)anions afford the (phenylthio)methyl complexes 1b and 2b, resulting from nucleophilic attack at the methyl group. 5b and 6b react with styrene to give phenylcyclopropane, free thioanisole, and the corresponding [M(OTf)(CO)(3)(bipy)] complex.
| Language | English |
|---|---|
| Pages | 5312-5319 |
| Number of pages | 8 |
| Journal | Organometallics |
| Volume | 21 |
| Issue number | 24 |
| DOIs | |
| Publication status | Published - 25 Nov 2002 |
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Keywords
- metal carbene complexes
- phase-transfer-catalysis
- crystal structures
- methylene transfer
- reagents
- cyclopropanation
- ligands
- photochemistry
Cite this
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Manganese(I) and rhenium(I) tricarbonyl (Alkylthio)methyl and alkylidenesulfonium complexes. / Hevia, E ; Perez, J ; Riera, V .
In: Organometallics, Vol. 21, No. 24, 25.11.2002, p. 5312-5319.Research output: Contribution to journal › Article
TY - JOUR
T1 - Manganese(I) and rhenium(I) tricarbonyl (Alkylthio)methyl and alkylidenesulfonium complexes
AU - Hevia, E
AU - Perez, J
AU - Riera, V
PY - 2002/11/25
Y1 - 2002/11/25
N2 - The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) compounds with ClCH2SR (R = Me, Ph) afford the (alkylthio)alkyl complexes [Mn(CH2SMe)(CO)(3)(bipy)] (1a), [Mn(CH2SPh)(CO)(3)-(bipy)] (1b), [Re(CH2SMe)(CO)(3)(bipy)] (2a), and [Re(CH2SMe)(CO)(3)(bipy)] (2b). Methylation at sulfur of these compounds with methyl triflate affords the methylidenesulfonium cations [Mn(CH2SMe2)(CO)(3)(bipy)](+) (5a), [Mn(CH2SMePh)(CO)(3)(bipy)](+) (5b), [Re(CH2SMe2)(CO)(3)(bipy)](+) (6a), and [Re(CH2SMePh)(CO)(3)(bipy)](+) (6b) as their triflate salts. These new compounds were characterized by IR and NMR spectroscopy, and the crystal structures of 1b, 2a, 5b, and 6b have been determined by X-ray diffraction. The sulfonium complexes are unreactive toward PPh3 and pyridine. The reactions of 5b and 6b with I-, PPh2-, and SEt(-)anions afford the (phenylthio)methyl complexes 1b and 2b, resulting from nucleophilic attack at the methyl group. 5b and 6b react with styrene to give phenylcyclopropane, free thioanisole, and the corresponding [M(OTf)(CO)(3)(bipy)] complex.
AB - The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) compounds with ClCH2SR (R = Me, Ph) afford the (alkylthio)alkyl complexes [Mn(CH2SMe)(CO)(3)(bipy)] (1a), [Mn(CH2SPh)(CO)(3)-(bipy)] (1b), [Re(CH2SMe)(CO)(3)(bipy)] (2a), and [Re(CH2SMe)(CO)(3)(bipy)] (2b). Methylation at sulfur of these compounds with methyl triflate affords the methylidenesulfonium cations [Mn(CH2SMe2)(CO)(3)(bipy)](+) (5a), [Mn(CH2SMePh)(CO)(3)(bipy)](+) (5b), [Re(CH2SMe2)(CO)(3)(bipy)](+) (6a), and [Re(CH2SMePh)(CO)(3)(bipy)](+) (6b) as their triflate salts. These new compounds were characterized by IR and NMR spectroscopy, and the crystal structures of 1b, 2a, 5b, and 6b have been determined by X-ray diffraction. The sulfonium complexes are unreactive toward PPh3 and pyridine. The reactions of 5b and 6b with I-, PPh2-, and SEt(-)anions afford the (phenylthio)methyl complexes 1b and 2b, resulting from nucleophilic attack at the methyl group. 5b and 6b react with styrene to give phenylcyclopropane, free thioanisole, and the corresponding [M(OTf)(CO)(3)(bipy)] complex.
KW - metal carbene complexes
KW - phase-transfer-catalysis
KW - crystal structures
KW - methylene transfer
KW - reagents
KW - cyclopropanation
KW - ligands
KW - photochemistry
U2 - 10.1021/om020522i
DO - 10.1021/om020522i
M3 - Article
VL - 21
SP - 5312
EP - 5319
JO - Organometallics
T2 - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 24
ER -