Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals

Ahmed M.H. Salem; Dina S. Hussein; Sara S. Terkawi; Audrey N. Stratton; Wei Yuan Chen; Briana R. Schrage; Kylin A. Emhoff; Masai M. Tate; Grace M. Minerovic; Christopher J. Ziegler; W. Christopher Boyd

doi:10.1016/j.ica.2024.122354

Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals

Ahmed M.H. Salem
, Dina S. Hussein
, Sara S. Terkawi
, Audrey N. Stratton
, Wei Yuan Chen
, Briana R. Schrage
, Kylin A. Emhoff
, Masai M. Tate
, Grace M. Minerovic
, Christopher J. Ziegler
, W. Christopher Boyd

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

1 Scopus citations

Abstract

The treatment of metal chlorides MCl₂ or metal chlorido complexes M(bpy)Cl₂ (M = Mn, Ni, Cu, bpy = 2,2′-bipyridyl) with TlPF₆ in acetonitrile to precipitate TlCl, followed by addition of excess nitrosobenzene, yielded monometallic or bimetallic azodioxide complex salts of the form [M(az)₄](PF₆)₂, [M(bpy)₂(az)](PF₆)₂, and [{M(bpy)(az)(μ-Cl)}₂](PF₆)₂ (az = cis-N,N′-diphenylazodioxide), which have been structurally characterized via single-crystal X-ray diffraction. The method of activation of chloride salts or chlorido complexes by chloride abstraction with Tl⁺, followed by the addition of nitrosobenzene, continues to be an effective strategy for the synthesis of azodioxide complexes, and it has enabled the synthesis of the first structurally characterized azodioxide complexes of any metals of Groups 7, 10, or 11.

Original language	English
Article number	122354
Journal	Inorganica Chimica Acta
Volume	574
DOIs	https://doi.org/10.1016/j.ica.2024.122354
State	Published - Jan 1 2025
Externally published	Yes

Funding

This research was supported by a Cleveland State University Faculty Innovative Research and Engagement award and a Cleveland State University Faculty Scholarship Initiative award to W.C.B., a Cleveland State University Graduate Student Research Award to A.M.H.S., and a Cleveland State University Graduate Student Research Award to K.A.E.

Keywords

Azodioxide
Copper
Manganese
Nickel
Octahedral coordination
Trigonal prismatic coordination

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10.1016/j.ica.2024.122354

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Salem, A. M. H., Hussein, D. S., Terkawi, S. S., Stratton, A. N., Chen, W. Y., Schrage, B. R., Emhoff, K. A., Tate, M. M., Minerovic, G. M., Ziegler, C. J., & Boyd, W. C. (2025). Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals. Inorganica Chimica Acta, 574, Article 122354. https://doi.org/10.1016/j.ica.2024.122354

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title = "Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals",

abstract = "The treatment of metal chlorides MCl2 or metal chlorido complexes M(bpy)Cl2 (M = Mn, Ni, Cu, bpy = 2,2′-bipyridyl) with TlPF6 in acetonitrile to precipitate TlCl, followed by addition of excess nitrosobenzene, yielded monometallic or bimetallic azodioxide complex salts of the form [M(az)4](PF6)2, [M(bpy)2(az)](PF6)2, and [\{M(bpy)(az)(μ-Cl)\}2](PF6)2 (az = cis-N,N′-diphenylazodioxide), which have been structurally characterized via single-crystal X-ray diffraction. The method of activation of chloride salts or chlorido complexes by chloride abstraction with Tl+, followed by the addition of nitrosobenzene, continues to be an effective strategy for the synthesis of azodioxide complexes, and it has enabled the synthesis of the first structurally characterized azodioxide complexes of any metals of Groups 7, 10, or 11.",

keywords = "Azodioxide, Copper, Manganese, Nickel, Octahedral coordination, Trigonal prismatic coordination",

author = "Salem, \{Ahmed M.H.\} and Hussein, \{Dina S.\} and Terkawi, \{Sara S.\} and Stratton, \{Audrey N.\} and Chen, \{Wei Yuan\} and Schrage, \{Briana R.\} and Emhoff, \{Kylin A.\} and Tate, \{Masai M.\} and Minerovic, \{Grace M.\} and Ziegler, \{Christopher J.\} and Boyd, \{W. Christopher\}",

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year = "2025",

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doi = "10.1016/j.ica.2024.122354",

language = "English",

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T1 - Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals

AU - Salem, Ahmed M.H.

AU - Hussein, Dina S.

AU - Terkawi, Sara S.

AU - Stratton, Audrey N.

AU - Chen, Wei Yuan

AU - Schrage, Briana R.

AU - Emhoff, Kylin A.

AU - Tate, Masai M.

AU - Minerovic, Grace M.

AU - Ziegler, Christopher J.

AU - Boyd, W. Christopher

PY - 2025/1/1

Y1 - 2025/1/1

N2 - The treatment of metal chlorides MCl2 or metal chlorido complexes M(bpy)Cl2 (M = Mn, Ni, Cu, bpy = 2,2′-bipyridyl) with TlPF6 in acetonitrile to precipitate TlCl, followed by addition of excess nitrosobenzene, yielded monometallic or bimetallic azodioxide complex salts of the form [M(az)4](PF6)2, [M(bpy)2(az)](PF6)2, and [{M(bpy)(az)(μ-Cl)}2](PF6)2 (az = cis-N,N′-diphenylazodioxide), which have been structurally characterized via single-crystal X-ray diffraction. The method of activation of chloride salts or chlorido complexes by chloride abstraction with Tl+, followed by the addition of nitrosobenzene, continues to be an effective strategy for the synthesis of azodioxide complexes, and it has enabled the synthesis of the first structurally characterized azodioxide complexes of any metals of Groups 7, 10, or 11.

AB - The treatment of metal chlorides MCl2 or metal chlorido complexes M(bpy)Cl2 (M = Mn, Ni, Cu, bpy = 2,2′-bipyridyl) with TlPF6 in acetonitrile to precipitate TlCl, followed by addition of excess nitrosobenzene, yielded monometallic or bimetallic azodioxide complex salts of the form [M(az)4](PF6)2, [M(bpy)2(az)](PF6)2, and [{M(bpy)(az)(μ-Cl)}2](PF6)2 (az = cis-N,N′-diphenylazodioxide), which have been structurally characterized via single-crystal X-ray diffraction. The method of activation of chloride salts or chlorido complexes by chloride abstraction with Tl+, followed by the addition of nitrosobenzene, continues to be an effective strategy for the synthesis of azodioxide complexes, and it has enabled the synthesis of the first structurally characterized azodioxide complexes of any metals of Groups 7, 10, or 11.

KW - Azodioxide

KW - Copper

KW - Manganese

KW - Nickel

KW - Octahedral coordination

KW - Trigonal prismatic coordination

UR - https://www.scopus.com/pages/publications/85202950915

U2 - 10.1016/j.ica.2024.122354

DO - 10.1016/j.ica.2024.122354

M3 - Article

AN - SCOPUS:85202950915

SN - 0020-1693

VL - 574

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

M1 - 122354

ER -

Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals

Abstract

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Keywords

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