Übertragung von Carbinliganden von Chrom auf Kobalt

Fischer, Ernst Otto; Däweritz, Albrecht

doi:10.1002/ange.19750870922

Cited by 14 publications

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References 11 publications

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“…[1][2][3][4] The first examples of compounds containing a transition metal triply bonded to a group 14 element were reported by Fischer and co-workers in 1973 as a series of transition metal-carbyne or -alkylidyne complexes of the general formula [RCt M(CO) 4 X] (R ) methyl (CH 3 or Me), phenyl (C 6 H 5 or Ph); M ) Cr, Mo, W; X ) Cl, Br, I) (1; Figure 1). 5 Two years later, Fischer and his co-workers also reported the synthesis and characterization of the first carbyne complex cation, [MeCt Cr(CO) 4 PMe 3 ] + (2), 6 and since then, the study of the chemistry of complexes containing MtC triple bonds (M ) transition metal) has matured into a thriving area of research. 1 One of the most recent highlights in the area, reported by Cummins and co-workers in 1997, was the isolation of the first carbide complex anion, [CtMo{N(R)R′} 3 ] -(R ) 2-methylhexadeuteriopropyl (C(CD 3 ) 2 Me); R′ ) 3,5-dimethylphenyl (3,5-Me 2 C 6 H 3 )) (3; Figure 1), which is the first compound featuring a one-coordinate carbon atom bonded to a metal center.…”

Section: Introductionmentioning

confidence: 99%

Triple Bonds between Transition Metals and the Heavier Elements of Groups 14 and 15

2007

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In the mid-1990s, the first examples of complexes containing triple bonds between transition metals and heavier analogues of the carbon as well as the nitrogen groups were reported, thus signaling the beginning of a new era in organometallic chemistry. Since then the progress in this field has been tremendous, with a large number of representative complexes being isolated and characterized. This review highlights the astonishing development of the chemistry of complexes containing triple bonds between transition metals and the heavier elements of groups 14 and 15 since its birth. The synthesis and the structural and spectroscopic features of these compounds are comprehensively discussed. Furthermore, the elucidation of their bonding modes by quantum-chemical methods as well as the relation between the reactivities of these complexes and their electronic structures are presented.

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Section: Introductionmentioning

confidence: 99%

Triple Bonds between Transition Metals and the Heavier Elements of Groups 14 and 15

2007

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Übergangsmetall‐Carbin‐Komplexe, IX: Umsetzungen von Pentacarbonyl(hydroxyorganylcarben)wolfram‐Komplexen mit Dicyclohexylcarbodiimid zu zweikernigen Carben‐Carbin‐Komplexen

Fischer¹,

Weiss²

1976

Chem. Ber.

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Pentacarbonyl(hydroxyorganylcarben)wolfram-Komplexe reagieren mit Dicyclohexylcarbodiimid(DCCD) unter intermolekularer Wasserabspaltung und Substitution des trans-standigen COLiganden durch einen Acylpentacarbonylmetallat-Rest zu zweikernigen Carben-Carbin-Komplexen 2 a -d und 3. Die Konstitutionsauflclarung der Carben-Carbin-Komplexe gelingt durch ihre IR-, 'H-NMR-und "C-NMR-Spektren, sowie durch ihre Reaktion mit Tetraalkylammoniumhalogeniden, die zu trans-Tetracarbonylhalogeno(organylcarbin)wolfram-Komplexen und Tetraalkylammonium-acylpentacarbonylmetallaten fuhrt. Transition Metal Carbyne Complexes, IX') Reaction of Pentaearbonyl(hydroxyorgany1carbene)tungsten Complexes with Dicyclohexylcarbodiimide (DCCD) to Form Binuclear Carbene Carbyne ComplexesPentacarbonyl(hydroxyorgany1carbene)tungsten complexes react with dicyclohexylcarbodiimide (DCCD) to yield the binuclear carbene carbyne complexes 2a -d and 3 by intermolecular elimination of water and substitution of the trans-CO-ligand by an acylpentacarbonylmetallate group. The constitution of the carbene carbyne complexes is elucidated by their i. r., 'H n. m. r., and 3C n. m. r. spectra and reactions with tetraalkylammonium halides, which produce trans-tetracarbonylhalogeno(organy1carbyne)tungsten complexes and tetraalkylammonium acylpentacarbonylmetallates. Praparative ErgebnisseViele der bekannten Reaktionen von Pentacarbonylcarbenkomplexen des Chroms lassen sich analog mit den homologem Pentacarbonylcarbenkomplexen des Wolframs durchfuhren. Beim Versuch, aus (CO)5WC(OH)C6H5 (1 a) mit DCCD in CH2Clz den Anhydridkomplex [(CO), WCC6H5]20 darzustellen, zeigte sich iiberraschend ein vollig anderer Reaktionsablauf als bei der entsprechenden Umsetzung von (CO)&~C(OH)C~HS mit DCCD, die zu [(C0)5CrCC6H5]z0 gefuhrt hatte'). Der (CO),W-Rest verhalt sich bei der " V111.

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Übergangsmetall‐Carbin‐Komplexe, XXXVIII: Carbinligandübertragung durch Umsetzung von neutralen und kationischen Carbinkomplexen mit Octacarbonyldicobalt oder Bis(π‐cyclopentadienyl)nickel

Fischer¹,

Däweritz²

1978

Chem. Ber.

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trans-Halogenotetracarbonyl(organylcarbin)chrom, -molybdan und -wolfram (1 -3) oder Dicarbonyl(x-cyclopentadienyl)(phenylcarbin)mangan-tetrachloroborat (4) reagieren unter sehr milden Bedingungen mit Octacarbonyldicobalt zu (a-Alkin)bis(tricarbonylcobalt) (Co -Co) (5) oder (p,-Alky1idin)-tris(tricarbonylcobalt)(Co -Co) (6). Mit Bis(x-cyclopentadieny1)nickel ergibt trans-Bromotetracarbonyl(pheny1carbin)chrom (1 b) unter den gleichen Bedingungen (x-To1an)-

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Übertragung von Carbinliganden von Chrom auf Kobalt

Cited by 14 publications

References 11 publications

Triple Bonds between Transition Metals and the Heavier Elements of Groups 14 and 15

Triple Bonds between Transition Metals and the Heavier Elements of Groups 14 and 15

Übergangsmetall‐Carbin‐Komplexe, IX: Umsetzungen von Pentacarbonyl(hydroxyorganylcarben)wolfram‐Komplexen mit Dicyclohexylcarbodiimid zu zweikernigen Carben‐Carbin‐Komplexen

Übergangsmetall‐Carbin‐Komplexe, XXXVIII: Carbinligandübertragung durch Umsetzung von neutralen und kationischen Carbinkomplexen mit Octacarbonyldicobalt oder Bis(π‐cyclopentadienyl)nickel

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