Tris(trimethylphosphine)cobalt(0) Compounds Containing Azaolefinic Ligands — Syntheses and Structures of Benzo[c]cinnoline and Phenylisocyanate Complexes

Mononuclear cobalt(0) complexes Co(η2-azaolefin)(PMe3)3 (azaolefin = benzo[c]cinnoline (1), p-dimethylamino-phenyl(phenyl)diazene (2), 1/2 diazobenzene (3), bis(p-tolyl)diazene (4), bis(p-fluorphenyl)diazene (5), bis(p-trifluoromethyl-phenyl)diazene (6), phenylisocyanate (7)) are obtained from Co(cyclo-C5H8)(PMe3)3 by substitution of the olefin. X-ray crystal structure determinations of 1 and 7 show tetrahedral arrangements of ligands around the cobalt atom. By reaction with carbon monoxide carbonyl(phosphine)cobalt(0) complexes are formed. 7 catalyses the cyclotrimerization of phenylisocyanate, while with CoCl(PMe3)3 as a catalyst the cyclic dimer of phenylisocyanate is selectively formed. A convenient synthesis for CoCl(PMe3)3 is described.

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Monoolefincobalt(0)-Komplexe / Monoolefincobalt(0) Complexes

Zeitschrift für Naturforschung B ◽

10.1515/znb-1988-1008 ◽

1988 ◽

Vol 43 (10) ◽

pp. 1256-1262 ◽

Cited By ~ 7

Author(s):

Hans-Friedrich Klein ◽

Goetz Lull ◽

Birgit Rodenhäuser ◽

Gerhard Cordier ◽

Helmut Paulus

Keyword(s):

Crystal Structure ◽

Carbon Monoxide ◽

Valence State ◽

Cobalt Atom ◽

Spectroscopic Properties ◽

X Ray ◽

Mononuclear Cobalt ◽

Structure Determinations

Mononuclear cobalt(o) complexes containing olefin and trimethylphosphane ligands Co(olefin)(PMe3)3 (olefin = C2H4 (1), C3H6 (2), cyclopentene (3), trans-1,2-diphenylethene (4), tetrafluorobenzo-bicyclo-(2.2.2)-octadiene (5)), are obtained from CoCl2 by reaction with magnesium in the presence of the ligands or by substitution of 3 with olefin. X-ray crystal structure determinations of 4 and 5 show a distorted tetrahedral arrangement of ligands around the cobalt atom. Chemical and spectroscopic properties are consistent with a paramagnetic valence state of the compounds in solution. By reaction with carbon monoxide a dicobalt complex is formed, while azobenzene gives paramagnetic Co(N2Ph2)(PMe3)2.

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Diolefincobalt(0)-Komplexe / Diolefincobalt(0) Complexes

Zeitschrift für Naturforschung B ◽

10.1515/znb-1984-0519 ◽

1984 ◽

Vol 39 (5) ◽

pp. 643-648 ◽

Cited By ~ 13

Author(s):

Hans-Friedrich Klein ◽

Joachim Groß ◽

Hubert Witty ◽

Dietmar Neugebauer

Keyword(s):

Crystal Structure ◽

Structure Determination ◽

Valence State ◽

Cobalt Atom ◽

Spectroscopic Properties ◽

Dinuclear Complex ◽

X Ray ◽

Linear Dimer ◽

Mononuclear Cobalt

Mononuclear cobalt(0) complexes containing diolefin and trimethylphosphane ligands Co(cycloocta-1,5-diene)(PMe3)2 and Co[(CH2=CHMe2Si)2O](PMe3)2 are obtained from CoCl2 by reaction with magnesium in the presence of the ligands or by substitution of cobalt(olefin)tris- (trimethylphosphane) with diolefin. Chemical and spectroscopic properties confirm the para- magnetic valence state of the compounds in solution. An X-Ray crystal structure determination of Co[(CH2=CHMe2Si)2O](PMe3)2 shows a tetrahedral arrangement of ligand functions around the cobalt atom. With butadiene a diamagnetic dinuclear complex [Co(C4H6)(PMe3)3]2 is obtained containing π-allyl co-ordination of two Co(PMe3)3 units to a linear dimer of butadiene

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