Zur komplexchemie von 4-zentren-π-systemen

Franz, Klaus‐Dieter; Dieck, Heindirk tom; Krynitz, U.; Renk, Ingo W.

doi:10.1016/s0022-328x(00)92184-3

Cited by 43 publications

(9 citation statements)

References 9 publications

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“…The EPR silence of 2 + at higher temperatures is remarkable since the DFT calculations show a spin density centered largely (70%) on the DAB ligand (Fig. S4) and DAB radical complexes have been easily observed at room temperature [29,33,[39][40][41][42][43]65,66]. The obviously rapid relaxation for 2 + , the deviation of g(average) = 2.036 from the free electron value of 2.0023 and the sizable splitting into well separated g components (g anisotropy g 1 À g 3 = 0.083) in the immobilized state are unusual for a radical anion complex [67] but are attributed to the interaction of the radical ligand with a heavy transition metal with a high spin-orbit coupling constant of about 3000 cm À1 [68].…”

Section: Spectroelectrochemistrymentioning

confidence: 96%

The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

Kaim

Sieger

Greulich

et al. 2010

Journal of Organometallic Chemistry

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Section: Spectroelectrochemistrymentioning

confidence: 96%

The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

Kaim

Sieger

Greulich

et al. 2010

Journal of Organometallic Chemistry

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“…" + HgCl2 -2KC1 + 2CO + (Mo(CO)3(DAB))2Hg (3) the structure of these complexes is assumed to be as given in Figure 4. The NMR spectra indicated the equivalence of the substituents on nitrogen which is in accordance with the proposed structure.…”

Section: K+ [Mo(co)4(d Ab) ]mentioning

confidence: 99%

Carbon-carbon bond formation between two .alpha.-diimines with the simultaneous formation of a metal-metal bond. X-ray structure of hexacarbonylbis[.mu.-(1-(isopropylamino)-2-(isopropylimino)ethano-N,N')]-dimolybdenum

Staal¹,

Oskam²,

Vrieze³

et al. 1979

Inorg. Chem.

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Reduction and subsequent oxidation of Mo(CO)4(DAB) (DAB = 1,4-diazabutadiene = -diimine) yield complexes with the formula Mo2(CO)6(IAE) (IAE = q-(l-(isopropylamino)-2-(isopropylimino)ethane-A,Ar)). Several methods were developed for the preparation of Mo2(CO)6(IAE) of which one involves a cyclic process with respect to Mn2(CO)10 and one a pseudocatalytic process with Hg2+ as catalyst. All methods have in common the oxidative elimination of CO from (Mo(CO)4(DAB))l resulting in the generation of the coordinative unsaturated Mo(CO)3(DAB) intermediate for which a structure containing a , -coordinated DAB ligand has been proposed. Dimerization of these 16-electron species yield the Mo2(CO)6(IAE) complexes. The X-ray crystal structure for the isopropyl derivative showed the formation of a carbon-carbon bond between two DAB ligands (1.61 (2) Á) and the formation of a short Mo-Mo single bond (2.813 (3) Á). The crystal was orthorhombic with space group R22,21 and cell constants a = 8.190 (1) Á, b = 10.099 (2) Á, c = 16.844 (2) A, and Z = 2.

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“…Der durch Elektronenübertragung aktivierte Komplex (1)~ wird als formaler 19-Elektronenkomplex vermutlich nur dissoziativ über (4)~ zu (5) abreagieren können, (6) + könnte aus (2)+ dagegen auch in einer SN2-Reaktion gebildet werden. Die "Reversibilität" der Redox-Reaktionen von (1) und (2) [1], [7], die sich während der Aufnahme hochaufgelöster ESRSpektren nicht verändern (Abb. 2).…”

Section: (6)unclassified

Zur Elektrochemie von Metall(O)-Verbindungen, V [1] Reaktionen von Diazadien-Metall(VIb)-carbonylkationen und -anionen / Electrochemistry of Metal(O) Compounds, V [1] Reactions of Diazadiene Metal(VIb) Carbonyl Cations and Anions

Dieck

Kühl

1982

Zeitschrift Für Naturforschung B

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Abstract Carbonyl complexes of chromium, molybdenum and tungsten of the type DAD M(CO)4 with DAD - diazadiene (R-N=CR′-CR′=NR) are shown by cyclic voltammetry to undergo electron transfer reactions to [DAD M(CO)4]+ and [DAD M(CO)4]-. The rate of subsequent chemical reactions with nucleophiles or by loss of ligands depend on the sol-vent, the metal and the ligands' electronic and steric properties. Chromium(+I) is more readily stabilized than Mo(+I) or W(-I) while the opposite is true for the stability of the anions formed. The dimerisation of a low-coordinate species DAD Mo(CO)3 from the reduction of DAD Mo(CO)3(CH3CN) is detected electrochemically. The stabilization of oxidation states +1 and -I is briefly discussed in view of the DAD ligand properties.

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Zur komplexchemie von 4-zentren-π-systemen

Cited by 43 publications

References 9 publications

The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

Carbon-carbon bond formation between two .alpha.-diimines with the simultaneous formation of a metal-metal bond. X-ray structure of hexacarbonylbis[.mu.-(1-(isopropylamino)-2-(isopropylimino)ethano-N,N')]-dimolybdenum

Zur Elektrochemie von Metall(O)-Verbindungen, V [1] Reaktionen von Diazadien-Metall(VIb)-carbonylkationen und -anionen / Electrochemistry of Metal(O) Compounds, V [1] Reactions of Diazadiene Metal(VIb) Carbonyl Cations and Anions

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