Manganese(I) and rhenium(I) tricarbonyl (Alkylthio)methyl and alkylidenesulfonium complexes

E Hevia, J Perez, V Riera

Research output: Contribution to journalArticle

8 Citations (Scopus)

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.

LanguageEnglish
Pages5312-5319
Number of pages8
JournalOrganometallics
Volume21
Issue number24
DOIs
Publication statusPublished - 25 Nov 2002

Fingerprint

Rhenium
rhenium
Carbon Monoxide
Manganese
manganese
methylation
styrenes
attack
pyridines
sulfur
anions
salts
cations
nuclear magnetic resonance
crystal structure
diffraction
spectroscopy
x rays
Sulfur Compounds
Styrene

Keywords

  • metal carbene complexes
  • phase-transfer-catalysis
  • crystal structures
  • methylene transfer
  • reagents
  • cyclopropanation
  • ligands
  • photochemistry

Cite this

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title = "Manganese(I) and rhenium(I) tricarbonyl (Alkylthio)methyl and alkylidenesulfonium complexes",
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.",
keywords = "metal carbene complexes, phase-transfer-catalysis, crystal structures, methylene transfer, reagents, cyclopropanation, ligands, photochemistry",
author = "E Hevia and J Perez and V Riera",
year = "2002",
month = "11",
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language = "English",
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pages = "5312--5319",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
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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 journalArticle

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 -