Iron complex compounds anions, carbonyl

Iron (II) complex compounds, anions, carbonyl, H2Fe(CO)4, and potassium salt, 2 243, 244... 

Anionic hydridoiron species undergo selective addition to a, -unsaturated earbonyl compounds in methanol to give reduction products (Noyori et al., 1972c). Under an atmosphere of carbon monoxide, carbonylation takes place. Methylmalonate is selectively obtained from acrylate by treatment of the reaction mixture with alcoholic iodine (Masada et al., 1970). The organo-iron complexes are readily acylated by treatment with alkyl iodides in an aprotic solvent (Mitsudo et al., 1974). 

The chemistry of the metal carbonyls has been the subject of hundreds of research papers, most of them appearing in the last decade of renaissance of inorganic chemistry. Reviews have appeared on the metal carbonyls themselves (/, 2) and on such related topics as the anionic carbonyl-metallates (S), metal-olefin complexes (4,5), tricarbonyl(diene)iron species (6), perfluoroalkyl metal compounds (7), andTr-cyclopentadienyl andir-arene (S, 9) metal derivatives. ... 

In a similar manner, Jt-allyl complexes of manganese, iron, and molybdenum carbonyls have been obtained from the corresponding metal carbonyl halides [5], In the case of the reaction of dicarbonyl(r 5-cyclopentadienyl)molybdenum bromide with allyl bromide, the c-allyl derivative is obtained in 75% yield in dichloromethane, but the Jt-allyl complex is the sole product (95%), when the reaction is conducted in a watenbenzene two-phase system. Similar solvent effects are observed in the corresponding reaction of the iron compound. As with the cobalt tetracarbonyl anion, it is... 

Oligo- and polymethylene-bridged complexes can be prepared by reaction of metal carbonyl anions with w.w -dihaloalkanes. This method proved to be a simple entry to the iron series /j,-(CH2)j.][(t75-C5H5) Fe(CO)2]2 (x s 3) (283), but yielded quite different products in the case of Na[(T 5-C5H5)Mo(CO)3] (283) and Na[Mn(CO)s] (284). An alternative two-step synthesis of the iron compounds involves the preparation of the mononuclear w-haloalkyls LXM—(CH2)X—X, and a subsequent... 

The most extensive series of compounds that fall within this section are the anionic iron carbonyl-thallium clusters recently described by Whitmire (30-30h). These are generally made by reactions between iron carbonylate anions and either T1(I) or Tl(III) salts. Thus treatment of K[HFe(CO)4] with a variety of thallium salts followed by addition of [Et4N]Cl or Br affords the hexanuclear complex [Et4N]2[ Fe(CO)4 2 //-TlFe(CO)4 2], 17... 

My co-worker J. Sedlmeier then held the view that the amine-containing iron carbonyl complexes were also ionic compounds (VII, 14, 21). Hence the compound Fe2(CO)4(en)3 (en= 1,2-ethylenediamine) was formulated as [Fe(en)3]2+[Fe(CO)4]2. Systematic investigations revealed that reactions of the iron carbonyls with other nitrogen and oxygen donors likewise involved valency disproportionation of the metal with concomitant formation of mono- and polynuclear carbonylferrates, viz., [Fe(CO)4]2, [Fe2(CO)8]2-, [Fe3(CO)n]2-. R. Werner (VII, 15, 17, 19, 20) even discovered and characterized compounds containing the tetranuclear anion [Fe4(CO)13]2, the first being that from pyridine and iron carbonyl, viz.,... 

On the other hand, polytellurides only seem to oxidize metals to the +1 or +11 state. Reaction of equimolar amounts of Te4 with M(CO)6 results in disubstitution of CO forming a cu-complex (CO)4MTe4 (M = Cr (45), W (47)47). If an excess of metal carbonyl is used in the presence of poly-telluride anion, multinuclear products can be isolated and metal-metal bonds can also form, leading to clusters. Careful manipulation of reaction conditions and choice of the polychalcogenide anion used makes possible partial oxidation of the metal centers and cluster formation. The reaction of iron carbonyls with polytelluride anions can lead to a wide array of cluster compounds, the identities of which are controlled by the stoichiometries and compositions of the starting telluride anions. For instance, reaction of [Fe(CO)5] with Te2 leads to the formation of [Fe3(CO)9(ju.3-Te)]2 (48),48 whereas its reaction with increasing amounts... 

Vanhoye and coworkers [402] synthesized aldehydes by using the electrogenerated radical anion of iron pentacarbonyl to reduce iodoethane and benzyl bromide in the presence of carbon monoxide. Esters can be prepared catalytically from alkyl halides and alcohols in the presence of iron pentacarbonyl [403]. Yoshida and coworkers reduced mixtures of organic halides and iron pentacarbonyl and then introduced an electrophile to obtain carbonyl compounds [404] and converted alkyl halides into aldehydes by using iron pentacarbonyl as a catalyst [405,406]. Finally, a review by Torii [407] provides references to additional papers that deal with catalytic processes involving complexes of nickel, cobalt, iron, palladium, rhodium, platinum, chromium, molybdenum, tungsten, manganese, rhenium, tin, lead, zinc, mercury, and titanium. 

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