Structural and mechanistic insights into s-block bimetallic catalysis: sodium magnesiate-catalyzed guanylation of amines

Marco De Tullio, Alberto Hernán-Gómez, Zoe Livingstone, William Clegg, Alan R. Kennedy, Ross W. Harrington, Antonio Antiñolo, Antonio Martínez, Fernando Carrillo-Hermosilla, Eva Hevia

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

To advance the catalytic applications of s-block mixed-metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed-metal system is much greater than that of its homometallic components [NaCH2SiMe3 ] and [Mg(CH2SiMe3)2]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N,N'-diisopropylcarbodiimide with 4-tert-butylaniline catalyzed by 1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine-assisted rate-determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle.

LanguageEnglish
Pages17646-17656
Number of pages11
JournalChemistry - A European Journal
Volume22
Issue number49
Early online date27 Oct 2016
DOIs
Publication statusPublished - 5 Dec 2016

Fingerprint

Carbodiimides
Catalysis
Amines
Sodium
Aniline Compounds
Catalysts
Kinetics
Aniline
Metal complexes
Amides
Coordination Complexes
Metals

Keywords

  • cooperative effects
  • guanidines
  • homogeneous catalysis
  • magnesiates
  • s-block metals
  • sodium magnesiate
  • hydrophosphination
  • carbodiimides
  • guanylation reactions

Cite this

De Tullio, Marco ; Hernán-Gómez, Alberto ; Livingstone, Zoe ; Clegg, William ; Kennedy, Alan R. ; Harrington, Ross W. ; Antiñolo, Antonio ; Martínez, Antonio ; Carrillo-Hermosilla, Fernando ; Hevia, Eva. / Structural and mechanistic insights into s-block bimetallic catalysis : sodium magnesiate-catalyzed guanylation of amines. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 49. pp. 17646-17656.
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abstract = "To advance the catalytic applications of s-block mixed-metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed-metal system is much greater than that of its homometallic components [NaCH2SiMe3 ] and [Mg(CH2SiMe3)2]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N,N'-diisopropylcarbodiimide with 4-tert-butylaniline catalyzed by 1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine-assisted rate-determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle.",
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De Tullio, M, Hernán-Gómez, A, Livingstone, Z, Clegg, W, Kennedy, AR, Harrington, RW, Antiñolo, A, Martínez, A, Carrillo-Hermosilla, F & Hevia, E 2016, 'Structural and mechanistic insights into s-block bimetallic catalysis: sodium magnesiate-catalyzed guanylation of amines' Chemistry - A European Journal, vol. 22, no. 49, pp. 17646-17656. https://doi.org/10.1002/chem.201602906

Structural and mechanistic insights into s-block bimetallic catalysis : sodium magnesiate-catalyzed guanylation of amines. / De Tullio, Marco; Hernán-Gómez, Alberto; Livingstone, Zoe; Clegg, William; Kennedy, Alan R.; Harrington, Ross W.; Antiñolo, Antonio; Martínez, Antonio; Carrillo-Hermosilla, Fernando; Hevia, Eva.

In: Chemistry - A European Journal, Vol. 22, No. 49, 05.12.2016, p. 17646-17656.

Research output: Contribution to journalArticle

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T1 - Structural and mechanistic insights into s-block bimetallic catalysis

T2 - Chemistry - A European Journal

AU - De Tullio, Marco

AU - Hernán-Gómez, Alberto

AU - Livingstone, Zoe

AU - Clegg, William

AU - Kennedy, Alan R.

AU - Harrington, Ross W.

AU - Antiñolo, Antonio

AU - Martínez, Antonio

AU - Carrillo-Hermosilla, Fernando

AU - Hevia, Eva

N1 - This is the peer reviewed version of the following article: De Tullio, M., Hernán-Gómez, A., Livingstone, Z., Clegg, W., Kennedy, A. R., Harrington, R. W., ... Hevia, E. (2016). Structural and mechanistic insights into s-block bimetallic catalysis: sodium magnesiate-catalyzed guanylation of amines. Chemistry - A European Journal, 22(49), 17646-17656, which has been published in final form at https://dx.doi.org/10.1002/chem.201602906. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

PY - 2016/12/5

Y1 - 2016/12/5

N2 - To advance the catalytic applications of s-block mixed-metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed-metal system is much greater than that of its homometallic components [NaCH2SiMe3 ] and [Mg(CH2SiMe3)2]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N,N'-diisopropylcarbodiimide with 4-tert-butylaniline catalyzed by 1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine-assisted rate-determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle.

AB - To advance the catalytic applications of s-block mixed-metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed-metal system is much greater than that of its homometallic components [NaCH2SiMe3 ] and [Mg(CH2SiMe3)2]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N,N'-diisopropylcarbodiimide with 4-tert-butylaniline catalyzed by 1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine-assisted rate-determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle.

KW - cooperative effects

KW - guanidines

KW - homogeneous catalysis

KW - magnesiates

KW - s-block metals

KW - sodium magnesiate

KW - hydrophosphination

KW - carbodiimides

KW - guanylation reactions

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U2 - 10.1002/chem.201602906

DO - 10.1002/chem.201602906

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VL - 22

SP - 17646

EP - 17656

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 49

ER -