Ein neues Additionsprodukt des Chrom (II)‐acetats: Diacetato‐dipyridyl‐bis‐isopropylamin‐chrom (II) [CrDipy(IPA)2(CH3COO)2]

Herzog, S.; Oberender, H.; Pahl, S.

doi:10.1002/zfch.19630030306

Cited by 8 publications

(10 citation statements)

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“…Solvents were dried and degassed using literature procedures. The complexes [Cr(bpy) 2 (CH 3 CO 2 ) 2 ] 0 ( 1 ) and [Cr(bpy)( i PrNH 2 ) 2 (CH 3 CO 2 ) 2 ] 0 ( 2 ), and the ligands 1,4-bis(cyclohexyl)-1,4-diaza-1,3-butadiene (DAD 0 ), 2-(2-trifluoromethyl)anilino-4,6-di- tert -butylphenol [CF 3 AP]H 2 , and 2,6-bis[1-(4-methoxyphenyliminoethyl)]pyridine (PDI 0 ) were prepared as previously described. The purity of the complexes was confirmed by elemental analyses.…”

Section: Methodsmentioning

confidence: 99%

“…It most certainly does not contain low-spin Cr II , as suggested in the original reports. 5,6 Finally, UKS calculations for neutral complex 2 (S = 1) converged exclusively to BS(3,1) solutions. The corresponding optimized geometry displayed excellent agreement with experiment, so contains a N,N′-coordinated bpy ligand that is clearly a π-radical anion.…”

Section: ⎯ → ⎯⎯⎯⎯mentioning

confidence: 99%

“…14 X-ray quality crystals were grown by slow evaporation of solvent from a concentrated acetone solution of complex. MS (EI+): m/z 1141 [5] [Cr( Me bpy) 3 ] 0 (7). To a stirring red-brown solution of [Cr 2 (μ-CH 3 CO 2 ) 4 ] 0 (340 mg, 1.0 mmol) in THF (20 mL) was added solid ( Me bpy 0 ) (737 mg, 4.0 mmol).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The presence of isopropylamine ( i PrNH 2 ) in the aforementioned reaction led to formation of a diff e r e n t a i r -s e n s i t i v e c o m p l e x , [ C r ( b p y ) -( i PrNH 2 ) 2 (CH 3 CO 2 ) 2 ] 0 (2, eq 2), which was also described as a low-spin Cr II species with an S = 1 ground state. 5 Complex 2 can also be obtained by addition of i PrNH 2 to solutions of 1 (eq 3).…”

Section: ■ Introductionmentioning

confidence: 99%

“…In 1963, Herzog et al reported that reaction of the dinuclear complex [Cr II 2 (μ-CH 3 CO 2 ) 4 ] 0 ·2THF (THF = tetrahydrofuran) with 4 equivalents of (bpy 0 ) in THF produces an air sensitive black powder corresponding to mononuclear [Cr(bpy) 2 (CH 3 CO 2 ) 2 ] 0 ( 1 , eq ), which has a magnetic moment of 3.01 μ B at ambient temperature in accord with a S = 1 ground state. , On this basis, the authors formulated 1 as a low-spin Cr II complex. The presence of isopropylamine ( i PrNH 2 ) in the aforementioned reaction led to formation of a different air-sensitive complex, [Cr(bpy)( i PrNH 2 ) 2 (CH 3 CO 2 ) 2 ] 0 ( 2 , eq ), which was also described as a low-spin Cr II species with an S = 1 ground state . Complex 2 can also be obtained by addition of i PrNH 2 to solutions of 1 (eq ). [ Cr 2 II ( μ ‐ CH 3 CO 2 ) 4 ] 0 + 4 false( bpy 0 false) → 2 [ Cr II ( bpy 0 ) 2 ( CH 3 CO 2 ) 2 ] 0 [ Cr 2 II ( μ ‐ CH 3 CO 2 ) 4 ] 0 + 4 i …”

Section: Introductionmentioning

confidence: 99%

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New Complexes of Chromium(III) Containing Organic π-Radical Ligands: An Experimental and Density Functional Theory Study

et al. 2013

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The electronic structures of a series of chromium complexes 1-7 have been experimentally investigated using a combination of X-ray crystallography, magneto- and electrochemistry, and Cr K-edge X-ray absorption and UV-vis spectroscopies. Reaction of the dimer [Cr(II)2(μ-CH3CO2)4](0) with 2,2'-bipyridine (bpy(0)) produced the complex [Cr(III)(bpy(0))(bpy(•))(CH3CO2)2](0) (S = 1) (1), but in the presence of isopropylamine ((i)PrNH2) [Cr(III)(bpy(•))((i)PrNH2)2(CH3CO2)2](0) (S = 1) (2) was obtained. Both 1 and 2 contain a Cr(III) ion and a single (bpy(•))(1-) ligand, so are not low-spin Cr(II) species. One-electron oxidation of 1 and 2 yielded [Cr(III)(bpy(0))2(CH3CO2)2]PF6 (S = 3/2) (3) in both cases. In addition, the new neutral species [Cr(III)(DAD(•))3](0) (S = 0) (4) and [Cr(III)(CF3AP(•))3](0) (S = 0) (5) have been synthesized. Both complexes contain three π-radical anion ligands, which derive from one electron reduction of 1,4-bis(cyclohexyl)-1,4-diaza-1,3-butadiene and one electron oxidation of 2-(2-trifluoromethyl)-anilino-4,6-di-tert-butylphenolate, respectively. Intramolecular antiferromagnetic coupling to d(3) Cr(III) gives the observed singlet ground states. Reaction of [Cr(II)(CH3CN)6](PF6)2 with 2,6-bis[1-(4-methoxyphenylimino)ethyl]pyridine (PDI(0)) under anaerobic conditions affords dark brown microcrystals of [Cr(III)(PDI(0))(PDI(•))](PF6)2 (S = 1) (6). This complex is shown to be a member of the electron transfer series [Cr(III)(PDI)2](3+/2+/1+/0), in which all one-electron transfer processes are ligand-based. By X-ray crystallography, it was shown that 6 possesses a localized electronic structure, such that one ligand is neutral (PDI(0)) and the other is a π-radical monoanion (PDI(•))(1-). Again, it should be highlighted that 6 is not a Cr(II) species. Lastly, the structure of [Cr(III)((Me)bpy(•))3](0) (S = 0) (7, (Me)bpy = 4,4'-dimethyl-2,2'-bipyridine) has been established by high resolution X-ray crystallography and clearly shows that three ((Me)bpy(•))(1-) radical anions are present. To further validate our electronic structure assignments, complexes 1-6 were investigated computationally using density functional theory (DFT) and found in all cases to contain a Cr(III) ion. This oxidation state assignment was experimentally confirmed for complexes 2, 4, 5, and 6 by Cr K-edge X-ray absorption spectroscopy.

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Section: Methodsmentioning

confidence: 99%

Section: ⎯ → ⎯⎯⎯⎯mentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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New Complexes of Chromium(III) Containing Organic π-Radical Ligands: An Experimental and Density Functional Theory Study

et al. 2013

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Darstellung und Eigenschaften von Chrom(II)‐carboxylaten. IV. Neue Addukte des Chrom(II)‐acetats und ‐formiats mit sauerstoff‐ und stickstoffhaltigen Liganden sowie Chrom(II)‐Salze substituierter Essigsäuren

Herzog

Kalies

1967

Zeitschrift anorg allge chemie

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Es werden Darstellung und Eigenschaften der folgenden neuen Chrom(II)‐Verbindungen mitgeteilt: Cr(CH3COO)2 · L (L = Essigsäure, Piperidin, α‐Picolin); Cr(HCOO)2 · L (L = Methanol, Tetrahydrofuran, 0,5 Dioxan, 2 HCOOH, Piperidin, α‐Picolin, Anilin, Acetonitril, Harnstoff, NH4HCOO, NH4Br); weiterhin Chrom(II)‐monochloracetat‐monohydrat, Chrom(II)‐trifluoracetat, Chrom(II)‐glycinat‐dihydrobromid‐dihydrat.

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Neue Chrom(II)‐verbindungen mit anomalen magnetischen Eigenschaften

Herzog

Kalies

1966

Zeitschrift fuer Chemie

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Ein neues Additionsprodukt des Chrom (II)‐acetats: Diacetato‐dipyridyl‐bis‐isopropylamin‐chrom (II) [CrDipy(IPA)₂(CH₃COO)₂]

Cited by 8 publications

References 1 publication

New Complexes of Chromium(III) Containing Organic π-Radical Ligands: An Experimental and Density Functional Theory Study

New Complexes of Chromium(III) Containing Organic π-Radical Ligands: An Experimental and Density Functional Theory Study

Darstellung und Eigenschaften von Chrom(II)‐carboxylaten. IV. Neue Addukte des Chrom(II)‐acetats und ‐formiats mit sauerstoff‐ und stickstoffhaltigen Liganden sowie Chrom(II)‐Salze substituierter Essigsäuren

Neue Chrom(II)‐verbindungen mit anomalen magnetischen Eigenschaften

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