Unsymmetrical Coordination of a Symmetrical 1,4‐Diazabutadiene to Iron(0)

Dieck, Heindirk tom; Orlopp, Alexander

doi:10.1002/anie.197502511

Cited by 28 publications

(2 citation statements)

References 7 publications

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“…However, in the phosphine system no competing reaction producing free ligand and Fe(CO) 5 was reported. Red, diamagnetic 14 is related to α-diimine iron tricarbonyl complexes reported by tom Dieck prepared by reaction of the free ligand with either Fe(CO) 5 under photochemical conditions or by thermal reaction with Fe 2 (CO) 9 . The corresponding reaction with the enantiopure dialkyl complex 8 resulted in clean formation of ketone along with free (−)-sparteine and Fe(CO) 5 , suggesting (−)-sparteine is not a good ligand for Fe(0).…”

Section: Resultsmentioning

confidence: 97%

Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

et al. 2003

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Synthesis and characterization of new, four-coordinate, high-spin iron(II) and manganese(II) complexes of the general form L2MR2 (L2 = neutral chelating ligand, R = alkyl) are described. Alkylation of the α-diimine complex, [ArNC(Me)−C(Me)NAr]FeCl2 (Ar = 2,6-diisopropylphenyl), as well as the enantiopure iron dichloride compounds, (−)-(sparteine)FeCl2 and (S)-(tBuBox)FeCl2 ((S)-(tBuBox) = 2,2-bis[2-[4(S)-(R‘)-1,3-oxazolinyl]propane), with LiCH2SiMe3 afforded the corresponding dialkyl derivatives. Solution magnetic susceptibility measurements and X-ray diffraction studies reveal each of the new iron(II) bis-trimethylsilylmethyl complexes to be high-spin, S = 2, tetrahedral molecules. In addition (−)-(sparteine)Fe(CH2CMe3)2, (−)-(sparteine)Fe(CH2C6H5)2, and (S)-(tBuBox)Fe(CH2C6H5)2 were also prepared and characterized by NMR spectroscopy and elemental analysis. An enantiopure, high-spin, tetrahedral manganese(II) dialkyl complex, (−)-(sparteine)Mn(CH2SiMe3)2, has also been synthesized. The catalytic activity of the new iron complexes in carbon−carbon bond forming processes has been evaluated, and stoichiometric reactions of the dialkyls with olefins, carbon monoxide, and the Lewis acid B(C6F5)3 have been examined.

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Section: Resultsmentioning

confidence: 97%

Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

et al. 2003

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“…-10 (7) -11 (6) -1 (8) N( 2 -18 (11) -53 (11) 5 (9) Multiplied by 104 and 10: respectively, for Mo and by 103 and 10, respectively, for all other atoms. case of the ether-THF mixture pentane had to be added) which was filtered off and washed twice with 50 mL of ether to yield 80% of (DAB)(CO)3Mo-Hg-Mo(CO)3(DAB).…”

Section: (1)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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Neue Verbindungen aus 1,4‐Diaza‐1,3‐dienen und Eisencarbonylen: Hexacarbonyl(1,4‐diazadien)dieisen und substituierte 2(3H)‐Imidazolone

et al. 1978

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Unsymmetrical Coordination of a Symmetrical 1,4‐Diazabutadiene to Iron(0)

Cited by 28 publications

References 7 publications

Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

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

Neue Verbindungen aus 1,4‐Diaza‐1,3‐dienen und Eisencarbonylen: Hexacarbonyl(1,4‐diazadien)dieisen und substituierte 2(3H)‐Imidazolone

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