Metal carbonyls halogens, reaction with

Certain metal carbonyls are very useful for the removal of halogens from polyhalogenated compounds. In these reactions, again, an oxidative addition step should be important. As shown below, carbenes 33>, cyclobutadiene 34>, and benzyne complexes 35> are formed by the dehalogenation reaction with metal carbonyls. 

Reactions of metal carbonyls with halogens lead to the formation of carbonyl halide complexes by substitution reactions or breaking metal-metal bonds. The reaction... 

Group IVA Donor Ligands. The anomalous reactions of PhaSiCl with metal carbonyl anions are discussed on p. 180. Only in the case of [Co(CO)3PPh3] was the normal substitution product obtained. GeH3Br reacts with Na-[Co(CO)4] in ether to produce [H3GeCo(CO)4]. The trideuterio-compound has also been prepared and spectroscopic properties reported for both compounds. The preparation and attempted preparation of halogen-bridged Ge-M compounds is referred to on pp. 180 and 200. In the case of cobalt. 

In cyclometalation reactions with metal compounds instead of the metal atoms discussed above, ligands such as hetero atom groups (e.g., bipyridines, phosphines, and carboxylates), unsaturated groups (e.g., aryl, allyl, Cp and Cp ), carbonyl groups, halogen atoms (F, Cl, Br, Cl), etc., also act as metal activators. 

STOPPED-FLOW MEASUREMENTS IN THE INFRARED SIMULATED RAPID SCAN SPECTRA SOME OBSERVATIONS ON THE REACTIONS OF METAL CARBONYL COMPOUNDS WITH HALOGEN. 

Pyridones can also be converted to 2-chloropyridines by exchanging the carbonyl functionality using phosphoroxychloride (POCI3) [72]. A combination of N-halosuccinimides and triphenylphosphine has also been applied to introduce halogens in this position [73]. The carbonyl functionality in 2-pyridones makes these systems reactive towards nucleophiles as well, which add in 1,4-reactions with displacement of halides [74]. The use of transition metal mediated couplings like Heck, and Suzuki have also been successfully applied on halogenated 2-pyridones (d. Scheme 10) [36,75]. 

Metal derivatives of cobalt carbonyl hydride such as Tl[Co(CO)4], Zn[Co(CO)4]2, or Cd[Co(CO)4]2 are formed upon reaction of cobalt octacarbonyl with these metals in the presence of carbon monoxide under pressure. Reaction with halogens (X) produces cobalt carbonyl halides, Co(CO)X2. 

The major route to -cyclopropenylium complexes L M(C3R3) (metallatetrahedranes) is by oxidative addition reactions of cyclopropenylium salts to transition metal complexes of groups 5 (V), 6 (Mo, W), 8 (Fe, Ru), 9 (Co, Rh, Ir) and 10 (Ni, Pd, Pt). The addition is frequently accompanied by loss of one or more carbonyl, olefin or halogen auxiliary ligand. Concurrent formation of oxocyclobutenyl complexes by carbonyl insertion into the cyclopropenyl ring is often observed in reactions with group 9 cobalt triad and early transition metal complexes. 

Reaction XLIV. (b) Condensation of Alkyl and Aryl Halogen Compounds with the Sodio- and other Metallo-derivatives of Ethyl Aceto-acetate and its Homolognes. (A., 186, 214 201, 143 213, 143.)—Like malonic ester, acetoacetic ester contains two 1 3-carbonyl groups with a methylene group in position 2. It is only to be expected then that it yields with metallic sodium or sodium alcoholate sodio-derivatives from which mono- and di-, alkyl and aryl homologues can be obtained by treatment with a suitable halide, including halogen esters. Acetoacetic acid... 

This review summarizes some earlier qualitative work as well as recent quantitative studies of redistribution equilibria and describes the principles underlying the mathematical treatment of such equilibria as well as the general implications of these equilibria with respect to general chemistry. In line with the general objective of the Advances in Organometallic Chemistry series, this article is limited to carbon-metal-bonded systems, metal hydrides, metal carbonyl compounds, metallocenes, and similar complexes. Excluded therefore are halogen-, sulfur-, nitrogen, and phosphorus-based systems.Various aspects of redistribution reactions were reviewed previously (42, 74, 87, 88,150,186, 285, 286, 288). 

In recent years more and more emphasis has been laid on the chemistry of cyclopentadienyl metal carbonyls. In this field the reactions of cyclopentadienyl metal carbonyl halides with electron donors deserve special attention. Many of these reactions yield cations by replacement of halogen. In the following report, general procedures will be described by which substituted cyclopentadienyliron dicarbonyl cations of the type [C5H5Fe(CO)2L]+ can be prepared. 

Similarly to the analogous reaction with furo[2,3-Z>]pyridines, metallation of compound (20) with n-butyllithium in TMEDA followed by the addition of DMF afforded the 2-formyl derivative in 66% yield. Likewise, metallation of the isomer (22) under the same conditions afforded the 2-formyl derivative in comparable yield <84JHC785>. Introduction of a carbonyl group at C-3 of compound (20) was accomplished by halogen-metal exchange between 3-bromothieno[2,3-6]pyridine and n-butyllithium. Table 45 lists some of the thieno[2,3-Z>]pyridine derivatives formed by this method <74JHC355>. 

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