π-Complexes of Lignols with Manganese(I) and Ruthenium(II)

Didier Morvan; Thomas B. Rauchfuss; Scott R. Wilson

doi:10.1021/om9001445

π-Complexes of Lignols with Manganese(I) and Ruthenium(II)

Didier Morvan, Thomas B. Rauchfuss, Scott R. Wilson

Chemistry

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Abstract

In view of contemporary interest in lignocellulose, we report the synthesis, structures, and preliminary reactivity of the first π-complexes of the lignin monomers (lignols). Initial studies with guaiacol demonstrated that it binds only weakly to Mo(CO) ₃ but [Mn(CO) ₃(guaiacol)] BF ₄ is robust. Related adducts with the cinnamyl alcohol derivatives, which are more closely related to the lignols, were unstable. From [Cp ^*Ru(MeCN) ₃]PF ₆, however, we generated the complete series of π-lignol complexes, including those from coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol as well as derivatives of ferulic and cinnamic acids. From a model dilignol derived from guaiacol and coniferyl alcohol was generated the expected mixture of π-complexes. Competition studies suggest that the allyl alcohol group on lignols does not influence the rate of π-complexation. Competition studies showed that [Cp ^*Ru(methylferulate)] ⁺ hydrolyzes faster than the free ester.

Original language	English (US)
Pages (from-to)	3161-3166
Number of pages	6
Journal	Organometallics
Volume	28
Issue number	11
DOIs	https://doi.org/10.1021/om9001445
State	Published - Jun 8 2009

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om9001445

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title = "π-Complexes of Lignols with Manganese(I) and Ruthenium(II)",

abstract = "In view of contemporary interest in lignocellulose, we report the synthesis, structures, and preliminary reactivity of the first π-complexes of the lignin monomers (lignols). Initial studies with guaiacol demonstrated that it binds only weakly to Mo(CO) 3 but [Mn(CO) 3(guaiacol)] BF 4 is robust. Related adducts with the cinnamyl alcohol derivatives, which are more closely related to the lignols, were unstable. From [Cp *Ru(MeCN) 3]PF 6, however, we generated the complete series of π-lignol complexes, including those from coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol as well as derivatives of ferulic and cinnamic acids. From a model dilignol derived from guaiacol and coniferyl alcohol was generated the expected mixture of π-complexes. Competition studies suggest that the allyl alcohol group on lignols does not influence the rate of π-complexation. Competition studies showed that [Cp *Ru(methylferulate)] + hydrolyzes faster than the free ester.",

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AU - Morvan, Didier

AU - Rauchfuss, Thomas B.

AU - Wilson, Scott R.

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Y1 - 2009/6/8

N2 - In view of contemporary interest in lignocellulose, we report the synthesis, structures, and preliminary reactivity of the first π-complexes of the lignin monomers (lignols). Initial studies with guaiacol demonstrated that it binds only weakly to Mo(CO) 3 but [Mn(CO) 3(guaiacol)] BF 4 is robust. Related adducts with the cinnamyl alcohol derivatives, which are more closely related to the lignols, were unstable. From [Cp *Ru(MeCN) 3]PF 6, however, we generated the complete series of π-lignol complexes, including those from coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol as well as derivatives of ferulic and cinnamic acids. From a model dilignol derived from guaiacol and coniferyl alcohol was generated the expected mixture of π-complexes. Competition studies suggest that the allyl alcohol group on lignols does not influence the rate of π-complexation. Competition studies showed that [Cp *Ru(methylferulate)] + hydrolyzes faster than the free ester.

AB - In view of contemporary interest in lignocellulose, we report the synthesis, structures, and preliminary reactivity of the first π-complexes of the lignin monomers (lignols). Initial studies with guaiacol demonstrated that it binds only weakly to Mo(CO) 3 but [Mn(CO) 3(guaiacol)] BF 4 is robust. Related adducts with the cinnamyl alcohol derivatives, which are more closely related to the lignols, were unstable. From [Cp *Ru(MeCN) 3]PF 6, however, we generated the complete series of π-lignol complexes, including those from coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol as well as derivatives of ferulic and cinnamic acids. From a model dilignol derived from guaiacol and coniferyl alcohol was generated the expected mixture of π-complexes. Competition studies suggest that the allyl alcohol group on lignols does not influence the rate of π-complexation. Competition studies showed that [Cp *Ru(methylferulate)] + hydrolyzes faster than the free ester.

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π-Complexes of Lignols with Manganese(I) and Ruthenium(II)

Abstract

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