Synthesis of open-shell, bimetallic Mn/Fe trinuclear clusters

Tamara M. Powers; Nina X. Gu; Alison R. Fout; Anne M. Baldwin; Raúl Hernández Sánchez; Denise M. Alfonso; Yu Sheng Chen; Shao Liang Zheng; Theodore A. Betley

doi:10.1021/ja408003d

Synthesis of open-shell, bimetallic Mn/Fe trinuclear clusters

Tamara M. Powers, Nina X. Gu, Alison R. Fout, Anne M. Baldwin, Raúl Hernández Sánchez, Denise M. Alfonso, Yu Sheng Chen, Shao Liang Zheng, Theodore A. Betley

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

Abstract

Concomitant deprotonation and metalation of hexadentate ligand platform ^tbsLH₆ (^tbsLH₆ = 1,3,5-C ₆H₉(NHC₆H₄-o-NHSiMe₂ ^tBu)₃) with divalent transition metal starting materials Fe₂(Mes)₄ (Mes = mesityl) or Mn₃(Mes) ₆ in the presence of tetrahydrofuran (THF) resulted in isolation of homotrinuclear complexes (^tbsL)Fe₃(THF) and ( ^tbsL)Mn₃(THF), respectively. In the absence of coordinating solvent (THF), the deprotonation and metalation exclusively afforded dinuclear complexes of the type (^tbsLH₂)M ₂ (M = Fe or Mn). The resulting dinuclear species were utilized as synthons to prepare bimetallic trinuclear clusters. Treatment of ( ^tbsLH₂)Fe₂ complex with divalent Mn source (Mn₂(N(SiMe₃)₂)₄) afforded the bimetallic complex (^tbsL)Fe₂Mn(THF), which established the ability of hexamine ligand ^tbsLH₆ to support mixed metal clusters. The substitutional homogeneity of (^tbsL)Fe ₂Mn(THF) was determined by ¹H NMR, ⁵⁷Fe Mössbauer, and X-ray fluorescence. Anomalous scattering measurements were critical for the unambiguous assignment of the trinuclear core composition. Heating a solution of (^tbsLH₂)Mn₂ with a stoichiometric amount of Fe₂(Mes)₄ (0.5 mol equiv) affords a mixture of both (^tbsL)Mn₂Fe(THF) and ( ^tbsL)Fe₂Mn(THF) as a result of the thermodynamic preference for heavier metal substitution within the hexa-anilido ligand framework. These results demonstrate for the first time the assembly of mixed metal cluster synthesis in an unbiased ligand platform.

Original language	English (US)
Pages (from-to)	14448-14458
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	135
Issue number	38
DOIs	https://doi.org/10.1021/ja408003d
State	Published - Sep 25 2013
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja408003d

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@article{efed5f4496fb41a8800176fca64b92fd,

title = "Synthesis of open-shell, bimetallic Mn/Fe trinuclear clusters",

abstract = "Concomitant deprotonation and metalation of hexadentate ligand platform tbsLH6 (tbsLH6 = 1,3,5-C 6H9(NHC6H4-o-NHSiMe2 tBu)3) with divalent transition metal starting materials Fe2(Mes)4 (Mes = mesityl) or Mn3(Mes) 6 in the presence of tetrahydrofuran (THF) resulted in isolation of homotrinuclear complexes (tbsL)Fe3(THF) and ( tbsL)Mn3(THF), respectively. In the absence of coordinating solvent (THF), the deprotonation and metalation exclusively afforded dinuclear complexes of the type (tbsLH2)M 2 (M = Fe or Mn). The resulting dinuclear species were utilized as synthons to prepare bimetallic trinuclear clusters. Treatment of ( tbsLH2)Fe2 complex with divalent Mn source (Mn2(N(SiMe3)2)4) afforded the bimetallic complex (tbsL)Fe2Mn(THF), which established the ability of hexamine ligand tbsLH6 to support mixed metal clusters. The substitutional homogeneity of (tbsL)Fe 2Mn(THF) was determined by 1H NMR, 57Fe M{\"o}ssbauer, and X-ray fluorescence. Anomalous scattering measurements were critical for the unambiguous assignment of the trinuclear core composition. Heating a solution of (tbsLH2)Mn2 with a stoichiometric amount of Fe2(Mes)4 (0.5 mol equiv) affords a mixture of both (tbsL)Mn2Fe(THF) and ( tbsL)Fe2Mn(THF) as a result of the thermodynamic preference for heavier metal substitution within the hexa-anilido ligand framework. These results demonstrate for the first time the assembly of mixed metal cluster synthesis in an unbiased ligand platform.",

author = "Powers, {Tamara M.} and Gu, {Nina X.} and Fout, {Alison R.} and Baldwin, {Anne M.} and {Hern{\'a}ndez S{\'a}nchez}, Ra{\'u}l and Alfonso, {Denise M.} and Chen, {Yu Sheng} and Zheng, {Shao Liang} and Betley, {Theodore A.}",

year = "2013",

month = sep,

day = "25",

doi = "10.1021/ja408003d",

language = "English (US)",

volume = "135",

pages = "14448--14458",

journal = "Journal of the American Chemical Society",

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T1 - Synthesis of open-shell, bimetallic Mn/Fe trinuclear clusters

AU - Powers, Tamara M.

AU - Gu, Nina X.

AU - Fout, Alison R.

AU - Baldwin, Anne M.

AU - Hernández Sánchez, Raúl

AU - Alfonso, Denise M.

AU - Chen, Yu Sheng

AU - Zheng, Shao Liang

AU - Betley, Theodore A.

PY - 2013/9/25

Y1 - 2013/9/25

N2 - Concomitant deprotonation and metalation of hexadentate ligand platform tbsLH6 (tbsLH6 = 1,3,5-C 6H9(NHC6H4-o-NHSiMe2 tBu)3) with divalent transition metal starting materials Fe2(Mes)4 (Mes = mesityl) or Mn3(Mes) 6 in the presence of tetrahydrofuran (THF) resulted in isolation of homotrinuclear complexes (tbsL)Fe3(THF) and ( tbsL)Mn3(THF), respectively. In the absence of coordinating solvent (THF), the deprotonation and metalation exclusively afforded dinuclear complexes of the type (tbsLH2)M 2 (M = Fe or Mn). The resulting dinuclear species were utilized as synthons to prepare bimetallic trinuclear clusters. Treatment of ( tbsLH2)Fe2 complex with divalent Mn source (Mn2(N(SiMe3)2)4) afforded the bimetallic complex (tbsL)Fe2Mn(THF), which established the ability of hexamine ligand tbsLH6 to support mixed metal clusters. The substitutional homogeneity of (tbsL)Fe 2Mn(THF) was determined by 1H NMR, 57Fe Mössbauer, and X-ray fluorescence. Anomalous scattering measurements were critical for the unambiguous assignment of the trinuclear core composition. Heating a solution of (tbsLH2)Mn2 with a stoichiometric amount of Fe2(Mes)4 (0.5 mol equiv) affords a mixture of both (tbsL)Mn2Fe(THF) and ( tbsL)Fe2Mn(THF) as a result of the thermodynamic preference for heavier metal substitution within the hexa-anilido ligand framework. These results demonstrate for the first time the assembly of mixed metal cluster synthesis in an unbiased ligand platform.

AB - Concomitant deprotonation and metalation of hexadentate ligand platform tbsLH6 (tbsLH6 = 1,3,5-C 6H9(NHC6H4-o-NHSiMe2 tBu)3) with divalent transition metal starting materials Fe2(Mes)4 (Mes = mesityl) or Mn3(Mes) 6 in the presence of tetrahydrofuran (THF) resulted in isolation of homotrinuclear complexes (tbsL)Fe3(THF) and ( tbsL)Mn3(THF), respectively. In the absence of coordinating solvent (THF), the deprotonation and metalation exclusively afforded dinuclear complexes of the type (tbsLH2)M 2 (M = Fe or Mn). The resulting dinuclear species were utilized as synthons to prepare bimetallic trinuclear clusters. Treatment of ( tbsLH2)Fe2 complex with divalent Mn source (Mn2(N(SiMe3)2)4) afforded the bimetallic complex (tbsL)Fe2Mn(THF), which established the ability of hexamine ligand tbsLH6 to support mixed metal clusters. The substitutional homogeneity of (tbsL)Fe 2Mn(THF) was determined by 1H NMR, 57Fe Mössbauer, and X-ray fluorescence. Anomalous scattering measurements were critical for the unambiguous assignment of the trinuclear core composition. Heating a solution of (tbsLH2)Mn2 with a stoichiometric amount of Fe2(Mes)4 (0.5 mol equiv) affords a mixture of both (tbsL)Mn2Fe(THF) and ( tbsL)Fe2Mn(THF) as a result of the thermodynamic preference for heavier metal substitution within the hexa-anilido ligand framework. These results demonstrate for the first time the assembly of mixed metal cluster synthesis in an unbiased ligand platform.

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Synthesis of open-shell, bimetallic Mn/Fe trinuclear clusters

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