Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Morris, Michael J.

doi:10.1016/b978-008046519-7.00044-7

Comprehensive Organometallic Chemistry II 1995

DOI: 10.1016/b978-008046519-7.00044-7

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Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Michael J. Morris

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1997

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Cited by 2 publications

References 1,329 publications

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Tungsten-Mediated Syntheses of Fused α-Methylenebutyrolactones from Propargyl Bromides Containing Tethered Aldehydes and Ketones

1997

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The reaction of CpW(CO)(3)Na with a number of propargyl bromides with tethered aldehydes and ketones afforded eta(1)-propargyl species that were subsequently transformed into tungsten-eta(3)-2-(methoxycarbonyl)allyl compounds upon treatment with p-TSA/CH(3)OH; the overall yields exceeded 60%. Sequential treatment of these tungsten-eta(3)-allyl complexes with NOBF(4) and NaI in CH(3)CN led to intramolecular allyltungsten-carbonyl cyclization, yielding fused alpha-methylene butyrolactones of five-, six-, and seven-membered carbocyclic rings. All the reactions proceeded with high diastereoselectivities except for 9-methylene-7-oxabicyclo[4.3.0]nonan-8-one (22) and 10-methylene-8-oxabicyclo[5.3.0]decan-9-one (23). Modification of the metal center with a chloride ligand led to significant improvement of the trans-stereoselection of 22; the chloride modification did not significantly enhance stereoselection of 23. The stereochemical course of the reaction products is rationalized on the basis of a bicyclic transition-state mechanism.

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Tungsten-Mediated Syntheses of Fused α-Methylenebutyrolactones from Propargyl Bromides Containing Tethered Aldehydes and Ketones

1997

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New Synthetic Pathway to Mono- and Bis-indenyl Complexes of Molybdenum(IV)

et al. 1998

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The complex IndMoCl3(CO)2 (Ind = η5-C9H7) has been synthesized by the reaction of IndMo(η3-C3H5)(CO)2 with HCl gas in dichloromethane at 25 °C. Thermal decarbonylation of IndMoCl3(CO)2 in chloroform gives paramagnetic IndMoCl3 (μeff = 1.48 μB). A consistent stepwise route to bis-indenyl derivatives of molybdenum is available upon treatment of IndMoCl3(CO)2 with KInd in THF at low temperature. The complex IndMo(η3-Ind)(CO)2 is obtained in high yield and opens a convenient entry into bis-indenyl molybdenum chemistry. The reaction of IndMo(η3-Ind)(CO)2 with Ph3CBF4, in CH2Cl2, yields [Ind2Mo(CO)2][BF4]2. Solvolysis of [Ind2Mo(CO)2][BF4]2 in acetonitrile affords [Ind2Mo(CO)(NCMe)][BF4]2 and [Ind2Mo(NCMe)2][BF4]2. The reaction of [Ind2Mo(NCMe)2][BF4]2 with [Bu4N][S2CNEt2] forms the dithiocarbamate complex [Ind2Mo(S2CNEt2)][BF4]. The molecular structures of IndMo(η3-Ind)(CO)2 and [Ind2Mo(S2CNEt2)][BF4] have been determined by single-crystal X-ray diffraction.

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Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Cited by 2 publications

References 1,329 publications

Tungsten-Mediated Syntheses of Fused α-Methylenebutyrolactones from Propargyl Bromides Containing Tethered Aldehydes and Ketones

Tungsten-Mediated Syntheses of Fused α-Methylenebutyrolactones from Propargyl Bromides Containing Tethered Aldehydes and Ketones

New Synthetic Pathway to Mono- and Bis-indenyl Complexes of Molybdenum(IV)

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