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M – C , M = C , M ≡ C

M – C , M = C , M ≡ C . 200901143 유대위. Contents. 1 st pick : Alkyl and related complexes 2 nd pick : Carbene complexes 3 rd pick : Carbyne ( Alkylidyne ) complexes 4 th pick (Duo) : Carbide and Cumulene complexes. M – C , M = C , M ≡ C. Alkyl and related complexes.

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M – C , M = C , M ≡ C

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  1. M – C , M = C , M ≡ C 200901143 유대위

  2. Contents • 1st pick : Alkyl and related complexes • 2nd pick : Carbene complexes • 3rd pick : Carbyne (Alkylidyne) complexes • 4th pick (Duo) • : Carbide and Cumulene complexes

  3. M – C , M = C , M ≡ C

  4. Alkyl and related complexes • Synthesis • 1. Reaction of a transition-metal halide with organoaluminum reagent • - M X + R A → M R + X A • Ex) ZrCl4 + 4PhCH2MgCl • → Zr(CH2Ph)4 + 4MgCl2 • 2. Reaction of a metal carbonyl anion with alkyl halide • Ex) Na[Mn(CO)5]¯ + CH3I • →CH3Mn(CO)5 + NaI

  5. Alkyl and related complexes • β - Hydride Elimination • - common side reaction

  6. Alkyl and related complexes • Bonds about alkyl ligands • Almost same as Alkane

  7. Alkyl and related complexes • It is not a alkyl ligand just using sigma bond

  8. Carbene Complexes and

  9. Carbene Complexes • Before we start explain about carbene complex • What is different between Carbene and Alkylidene ? • Simply Fischer discovered the carbene, and lately Schrock discovered the different carbene. So he gave this name ‘Alkylidene’ • So we can say Schrock carbene, Schrock alkylidene • It is same at ‘carbyne’ and ‘alkylidyne’

  10. Carbene Complexes

  11. Carbene Complexes Fischer Carbenesfavor the weak bonding situation, where the metal has a d6 configuration (counting the carbene as neutral ligand), CO ligands, and the carbene has -donating groups. The d6 configuration naturally favors the middle to late transition metals.

  12. Carbene Complexes • Such a delocalized 3-atom system provides more stability to the bonding Pi electonpari than would a simple metal-to-carbon Pi bond

  13. Carbene Complexes • Intersting things in methoxycarbene complex Cr(CO)5[C(OCH3)C6H5] • 2 peaks appeared in this compound • (at High tempearture and Low temperature)

  14. Carbyne Complexes • Carbyne complexes have metal-carbon triple bonds they; thay are formally analogous to alkynes • M ≡ C - R

  15. Carbyne Complexes

  16. Carbyne Complexes Same as CO ligands

  17. Carbide and Cumulene • There are –CR3 , =CR2 , ≡CR3 and to assign a quadruple bond to carbon, but evidence described as M ≡ C ¯ ☞ Carbide

  18. Carbide and Cumulene • Ligands with chains of carbon atoms that have cumulated (consecutive) double bonds, designated cumulenyldieneligands

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