Oxidative group transfer to a triiron complex to form a nucleophilic μ3-nitride, [Fe3(μ3-N)]-

Tamara M. Powers; Alison R. Fout; Shao Liang Zheng; Theodore A. Betley

doi:10.1021/ja2003445

Oxidative group transfer to a triiron complex to form a nucleophilic μ³-nitride, [Fe₃(μ³-N)]^-

Tamara M. Powers, Alison R. Fout, Shao Liang Zheng, Theodore A. Betley

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

Abstract

Utilizing a hexadentate ligand platform, a high-spin trinuclear iron complex of the type (^tbsL)Fe₃(thf) was synthesized and characterized ([^tbsL]^6- = [1,3,5-C₆H ₉(NPh-o-NSi^tBuMe₂)₃]^6-). The silyl-amide groups only permit ligation of one solvent molecule to the tri-iron core, resulting in an asymmetric core wherein each iron ion exhibits a distinct local coordination environment. The triiron complex ( ^tbsL)Fe₃(thf) rapidly consumes inorganic azide ([N ₃]NBu₄) to afford an anionic, trinuclear nitride complex [(^tbsL)Fe₃(μ³-N)]NBu₄. The nearly C₃-symmetric complex exhibits a highly pyramidalized nitride ligand that resides 1.205(3) Å above the mean triiron plane with short Fe-N (1.871(3) Å) distances and Fe-Fe separation (2.480(1) Å). The nucleophilic nitride can be readily alkylated via reaction with methyl iodide to afford the neutral, trinuclear methylimide complex (^tbsL)Fe ₃(μ³-NCH₃). Alkylation of the nitride maintains the approximate C₃-symmetry in the imide complex, where the imide ligand resides 1.265(9) Å above the mean triiron plane featuring lengthened Fe-N_imide bond distances (1.892(3) Å) with nearly equal Fe-Fe separation (2.483(1) Å).

Original language	English (US)
Pages (from-to)	3336-3338
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	133
Issue number	10
DOIs	https://doi.org/10.1021/ja2003445
State	Published - Mar 16 2011
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Online availability

10.1021/ja2003445

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Cite this

@article{f5014acf1a21414baf8d45d342c03098,

title = "Oxidative group transfer to a triiron complex to form a nucleophilic μ3-nitride, [Fe3(μ3-N)]-",

abstract = "Utilizing a hexadentate ligand platform, a high-spin trinuclear iron complex of the type (tbsL)Fe3(thf) was synthesized and characterized ([tbsL]6- = [1,3,5-C6H 9(NPh-o-NSitBuMe2)3]6-). The silyl-amide groups only permit ligation of one solvent molecule to the tri-iron core, resulting in an asymmetric core wherein each iron ion exhibits a distinct local coordination environment. The triiron complex ( tbsL)Fe3(thf) rapidly consumes inorganic azide ([N 3]NBu4) to afford an anionic, trinuclear nitride complex [(tbsL)Fe3(μ3-N)]NBu4. The nearly C3-symmetric complex exhibits a highly pyramidalized nitride ligand that resides 1.205(3) {\AA} above the mean triiron plane with short Fe-N (1.871(3) {\AA}) distances and Fe-Fe separation (2.480(1) {\AA}). The nucleophilic nitride can be readily alkylated via reaction with methyl iodide to afford the neutral, trinuclear methylimide complex (tbsL)Fe 3(μ3-NCH3). Alkylation of the nitride maintains the approximate C3-symmetry in the imide complex, where the imide ligand resides 1.265(9) {\AA} above the mean triiron plane featuring lengthened Fe-Nimide bond distances (1.892(3) {\AA}) with nearly equal Fe-Fe separation (2.483(1) {\AA}).",

author = "Powers, {Tamara M.} and Fout, {Alison R.} and Zheng, {Shao Liang} and Betley, {Theodore A.}",

year = "2011",

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doi = "10.1021/ja2003445",

language = "English (US)",

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journal = "Journal of the American Chemical Society",

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AU - Powers, Tamara M.

AU - Fout, Alison R.

AU - Zheng, Shao Liang

AU - Betley, Theodore A.

PY - 2011/3/16

Y1 - 2011/3/16

N2 - Utilizing a hexadentate ligand platform, a high-spin trinuclear iron complex of the type (tbsL)Fe3(thf) was synthesized and characterized ([tbsL]6- = [1,3,5-C6H 9(NPh-o-NSitBuMe2)3]6-). The silyl-amide groups only permit ligation of one solvent molecule to the tri-iron core, resulting in an asymmetric core wherein each iron ion exhibits a distinct local coordination environment. The triiron complex ( tbsL)Fe3(thf) rapidly consumes inorganic azide ([N 3]NBu4) to afford an anionic, trinuclear nitride complex [(tbsL)Fe3(μ3-N)]NBu4. The nearly C3-symmetric complex exhibits a highly pyramidalized nitride ligand that resides 1.205(3) Å above the mean triiron plane with short Fe-N (1.871(3) Å) distances and Fe-Fe separation (2.480(1) Å). The nucleophilic nitride can be readily alkylated via reaction with methyl iodide to afford the neutral, trinuclear methylimide complex (tbsL)Fe 3(μ3-NCH3). Alkylation of the nitride maintains the approximate C3-symmetry in the imide complex, where the imide ligand resides 1.265(9) Å above the mean triiron plane featuring lengthened Fe-Nimide bond distances (1.892(3) Å) with nearly equal Fe-Fe separation (2.483(1) Å).

AB - Utilizing a hexadentate ligand platform, a high-spin trinuclear iron complex of the type (tbsL)Fe3(thf) was synthesized and characterized ([tbsL]6- = [1,3,5-C6H 9(NPh-o-NSitBuMe2)3]6-). The silyl-amide groups only permit ligation of one solvent molecule to the tri-iron core, resulting in an asymmetric core wherein each iron ion exhibits a distinct local coordination environment. The triiron complex ( tbsL)Fe3(thf) rapidly consumes inorganic azide ([N 3]NBu4) to afford an anionic, trinuclear nitride complex [(tbsL)Fe3(μ3-N)]NBu4. The nearly C3-symmetric complex exhibits a highly pyramidalized nitride ligand that resides 1.205(3) Å above the mean triiron plane with short Fe-N (1.871(3) Å) distances and Fe-Fe separation (2.480(1) Å). The nucleophilic nitride can be readily alkylated via reaction with methyl iodide to afford the neutral, trinuclear methylimide complex (tbsL)Fe 3(μ3-NCH3). Alkylation of the nitride maintains the approximate C3-symmetry in the imide complex, where the imide ligand resides 1.265(9) Å above the mean triiron plane featuring lengthened Fe-Nimide bond distances (1.892(3) Å) with nearly equal Fe-Fe separation (2.483(1) Å).

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