Filling a Gap: Electrochemical Property Comparison of the Completed Compound Series [Mo2(DArF)n(O2C-Fc)4-n] (DArF = N,N′-Diarylformamidinate; O2C-Fc = Ferrocenecarboxylate)

Xu Min Cai; Teresa K. Meister; Alexander Pöthig; Fritz E. Kühn

doi:10.1021/acs.inorgchem.5b02329

Filling a Gap: Electrochemical Property Comparison of the Completed Compound Series [Mo₂(DArF)_n(O₂C-Fc)_4-n] (DArF = N,N′-Diarylformamidinate; O₂C-Fc = Ferrocenecarboxylate)

Xu Min Cai, Teresa K. Meister, Alexander Pöthig, Fritz E. Kühn

Associate Professorship of Molecular Catalysis

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

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Abstract

The reaction of cis-[Mo₂(O₂C-Fc)₂(NCCH₃)₄][BF₄]₂ (cis-1) with two electronically different N,N′-diarylformamidinate (DArF) ligands (DArF = N,N′-bis(p-trifluoromethylphenyl)formamidinate (DTfmpF), N,N′-bis(p-anisyl)formamidinate (DAniF)) results in the isolation of the tris- and monosubstituted complexes [Mo₂(DTfmpF)₃(O₂C-Fc)] (2a) and [Mo₂(DAniF)(O₂C-Fc)₃] (2b). These complexes complete the series of [Mo₂(DArF)_n(O₂C-Fc)_4-n] (n = 4-0) type compounds, thus allowing for a comprehensive study. On the basis of the oxidation potential E_1/2([Mo₂]⁴⁺/[Mo₂]⁵⁺) of all Mo₂ complexes, ligand basicity is found to decrease in the order DAniF^- > DTfmpF^- > Fc-CO₂^- 蠑 CH₃CN. In addition, no direct electronic interaction between the trans-positioned Fc units in complex 2b is detected, which is attributed to the full overlap of all Fc oxidation processes. Furthermore, the low-energy absorption bands of compounds 2a,b are located at different positions in their respective UV-vis spectra.

Original language	English
Pages (from-to)	858-864
Number of pages	7
Journal	Inorganic Chemistry
Volume	55
Issue number	2
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02329
State	Published - 19 Jan 2016

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@article{b5b3acbc3ec4402a8517a722b50c8931,

title = "Filling a Gap: Electrochemical Property Comparison of the Completed Compound Series [Mo2(DArF)n(O2C-Fc)4-n] (DArF = N,N′-Diarylformamidinate; O2C-Fc = Ferrocenecarboxylate)",

abstract = "The reaction of cis-[Mo2(O2C-Fc)2(NCCH3)4][BF4]2 (cis-1) with two electronically different N,N′-diarylformamidinate (DArF) ligands (DArF = N,N′-bis(p-trifluoromethylphenyl)formamidinate (DTfmpF), N,N′-bis(p-anisyl)formamidinate (DAniF)) results in the isolation of the tris- and monosubstituted complexes [Mo2(DTfmpF)3(O2C-Fc)] (2a) and [Mo2(DAniF)(O2C-Fc)3] (2b). These complexes complete the series of [Mo2(DArF)n(O2C-Fc)4-n] (n = 4-0) type compounds, thus allowing for a comprehensive study. On the basis of the oxidation potential E1/2([Mo2]4+/[Mo2]5+) of all Mo2 complexes, ligand basicity is found to decrease in the order DAniF- > DTfmpF- > Fc-CO2- 蠑 CH3CN. In addition, no direct electronic interaction between the trans-positioned Fc units in complex 2b is detected, which is attributed to the full overlap of all Fc oxidation processes. Furthermore, the low-energy absorption bands of compounds 2a,b are located at different positions in their respective UV-vis spectra.",

author = "Cai, {Xu Min} and Meister, {Teresa K.} and Alexander P{\"o}thig and K{\"u}hn, {Fritz E.}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2016",

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doi = "10.1021/acs.inorgchem.5b02329",

language = "English",

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T1 - Filling a Gap

T2 - Electrochemical Property Comparison of the Completed Compound Series [Mo2(DArF)n(O2C-Fc)4-n] (DArF = N,N′-Diarylformamidinate; O2C-Fc = Ferrocenecarboxylate)

AU - Cai, Xu Min

AU - Meister, Teresa K.

AU - Pöthig, Alexander

AU - Kühn, Fritz E.

PY - 2016/1/19

Y1 - 2016/1/19

N2 - The reaction of cis-[Mo2(O2C-Fc)2(NCCH3)4][BF4]2 (cis-1) with two electronically different N,N′-diarylformamidinate (DArF) ligands (DArF = N,N′-bis(p-trifluoromethylphenyl)formamidinate (DTfmpF), N,N′-bis(p-anisyl)formamidinate (DAniF)) results in the isolation of the tris- and monosubstituted complexes [Mo2(DTfmpF)3(O2C-Fc)] (2a) and [Mo2(DAniF)(O2C-Fc)3] (2b). These complexes complete the series of [Mo2(DArF)n(O2C-Fc)4-n] (n = 4-0) type compounds, thus allowing for a comprehensive study. On the basis of the oxidation potential E1/2([Mo2]4+/[Mo2]5+) of all Mo2 complexes, ligand basicity is found to decrease in the order DAniF- > DTfmpF- > Fc-CO2- 蠑 CH3CN. In addition, no direct electronic interaction between the trans-positioned Fc units in complex 2b is detected, which is attributed to the full overlap of all Fc oxidation processes. Furthermore, the low-energy absorption bands of compounds 2a,b are located at different positions in their respective UV-vis spectra.

AB - The reaction of cis-[Mo2(O2C-Fc)2(NCCH3)4][BF4]2 (cis-1) with two electronically different N,N′-diarylformamidinate (DArF) ligands (DArF = N,N′-bis(p-trifluoromethylphenyl)formamidinate (DTfmpF), N,N′-bis(p-anisyl)formamidinate (DAniF)) results in the isolation of the tris- and monosubstituted complexes [Mo2(DTfmpF)3(O2C-Fc)] (2a) and [Mo2(DAniF)(O2C-Fc)3] (2b). These complexes complete the series of [Mo2(DArF)n(O2C-Fc)4-n] (n = 4-0) type compounds, thus allowing for a comprehensive study. On the basis of the oxidation potential E1/2([Mo2]4+/[Mo2]5+) of all Mo2 complexes, ligand basicity is found to decrease in the order DAniF- > DTfmpF- > Fc-CO2- 蠑 CH3CN. In addition, no direct electronic interaction between the trans-positioned Fc units in complex 2b is detected, which is attributed to the full overlap of all Fc oxidation processes. Furthermore, the low-energy absorption bands of compounds 2a,b are located at different positions in their respective UV-vis spectra.

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DO - 10.1021/acs.inorgchem.5b02329

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SN - 0020-1669

VL - 55

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JO - Inorganic Chemistry

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ER -

Filling a Gap: Electrochemical Property Comparison of the Completed Compound Series [Mo₂(DArF)_n(O₂C-Fc)_4-n] (DArF = N,N′-Diarylformamidinate; O₂C-Fc = Ferrocenecarboxylate)

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