Nitro and Nitrato Complexes of Cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III). Preparation and Use as Oxidants

Ronald P. Wirth; Larry L. Miller; Wayne L Gladfelter

doi:10.1021/om50005a029

Nitro and Nitrato Complexes of Cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III). Preparation and Use as Oxidants

Ronald P. Wirth, Larry L. Miller, Wayne L Gladfelter

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

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Abstract

The preparation of a series of cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III) complexes, CpCo(S₂CNR₂)X (R = CH₃, C₂H₅; X = I, N0₂, N0₃) and [CpCo(S₂CN(CH₃)₂)L]X (L = Ph₃P, X = I, BF₄; L = CH₃CN, X = BF₄), is described. Mixtures of CpCo(S₂CN(CH₃)₂)NO₂ and BF₃-Et₂O were found to oxidize benzyl alcohol to benzaldehyde. The reaction is stoichiometric in the absence of oxygen. Benzyl alcohol is also oxidized by mixtures of CpCo(S₂CN(CH₃)₂)N0₃, PPNN0₂, and PPNN0₃ (PPN = (Ph₃P)₂N) with BF₃-Et₂O. The oxidations by the nitrate species are catalytic in the presence of oxygen. The detailed results rule out mechanisms for the metal nitro complex reactions that involve metal-bound nitrogen oxide ester intermediates. A mechanism in which NO₂- reacts with BF₃ to give the actual oxidant is proposed.

Original language	English (US)
Pages (from-to)	1649-1654
Number of pages	6
Journal	Organometallics
Volume	2
Issue number	11
DOIs	https://doi.org/10.1021/om50005a029
State	Published - Nov 1983

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@article{55d98df0e2d94576b51da308816091c3,

title = "Nitro and Nitrato Complexes of Cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III). Preparation and Use as Oxidants",

abstract = "The preparation of a series of cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III) complexes, CpCo(S2CNR2)X (R = CH3, C2H5; X = I, N02, N03) and [CpCo(S2CN(CH3)2)L]X (L = Ph3P, X = I, BF4; L = CH3CN, X = BF4), is described. Mixtures of CpCo(S2CN(CH3)2)NO2 and BF3-Et2O were found to oxidize benzyl alcohol to benzaldehyde. The reaction is stoichiometric in the absence of oxygen. Benzyl alcohol is also oxidized by mixtures of CpCo(S2CN(CH3)2)N03, PPNN02, and PPNN03 (PPN = (Ph3P)2N) with BF3-Et2O. The oxidations by the nitrate species are catalytic in the presence of oxygen. The detailed results rule out mechanisms for the metal nitro complex reactions that involve metal-bound nitrogen oxide ester intermediates. A mechanism in which NO2- reacts with BF3 to give the actual oxidant is proposed.",

author = "Wirth, {Ronald P.} and Miller, {Larry L.} and Gladfelter, {Wayne L}",

year = "1983",

month = nov,

doi = "10.1021/om50005a029",

language = "English (US)",

volume = "2",

pages = "1649--1654",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - Nitro and Nitrato Complexes of Cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III). Preparation and Use as Oxidants

AU - Wirth, Ronald P.

AU - Miller, Larry L.

AU - Gladfelter, Wayne L

PY - 1983/11

Y1 - 1983/11

N2 - The preparation of a series of cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III) complexes, CpCo(S2CNR2)X (R = CH3, C2H5; X = I, N02, N03) and [CpCo(S2CN(CH3)2)L]X (L = Ph3P, X = I, BF4; L = CH3CN, X = BF4), is described. Mixtures of CpCo(S2CN(CH3)2)NO2 and BF3-Et2O were found to oxidize benzyl alcohol to benzaldehyde. The reaction is stoichiometric in the absence of oxygen. Benzyl alcohol is also oxidized by mixtures of CpCo(S2CN(CH3)2)N03, PPNN02, and PPNN03 (PPN = (Ph3P)2N) with BF3-Et2O. The oxidations by the nitrate species are catalytic in the presence of oxygen. The detailed results rule out mechanisms for the metal nitro complex reactions that involve metal-bound nitrogen oxide ester intermediates. A mechanism in which NO2- reacts with BF3 to give the actual oxidant is proposed.

AB - The preparation of a series of cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III) complexes, CpCo(S2CNR2)X (R = CH3, C2H5; X = I, N02, N03) and [CpCo(S2CN(CH3)2)L]X (L = Ph3P, X = I, BF4; L = CH3CN, X = BF4), is described. Mixtures of CpCo(S2CN(CH3)2)NO2 and BF3-Et2O were found to oxidize benzyl alcohol to benzaldehyde. The reaction is stoichiometric in the absence of oxygen. Benzyl alcohol is also oxidized by mixtures of CpCo(S2CN(CH3)2)N03, PPNN02, and PPNN03 (PPN = (Ph3P)2N) with BF3-Et2O. The oxidations by the nitrate species are catalytic in the presence of oxygen. The detailed results rule out mechanisms for the metal nitro complex reactions that involve metal-bound nitrogen oxide ester intermediates. A mechanism in which NO2- reacts with BF3 to give the actual oxidant is proposed.

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JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 11

ER -

Nitro and Nitrato Complexes of Cyclopentadienyl(N,N-dialkyldithiocarbamato)cobalt(III). Preparation and Use as Oxidants

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