Carbonyl complexes, chromium cobalt

Transition metal complexes which react with diazoalkanes to yield carbene complexes can be catalysts for diazodecomposition (see Section 4.1). In addition to the requirements mentioned above (free coordination site, electrophi-licity), transition metal complexes can catalyze the decomposition of diazoalkanes if the corresponding carbene complexes are capable of transferring the carbene fragment to a substrate with simultaneous regeneration of the original complex. Metal carbonyls of chromium, iron, cobalt, nickel, molybdenum, and tungsten all catalyze the decomposition of diazomethane [493]. Other related catalysts are (CO)5W=C(OMe)Ph [509], [Cp(CO)2Fe(THF)][BF4] [510,511], and (CO)5Cr(COD) [52,512]. These compounds are sufficiently electrophilic to catalyze the decomposition of weakly nucleophilic, acceptor-substituted diazoalkanes. 

In 1980 we published a survey (1) of our major results in this area as of late 1979. These results include extensive work on binuclear CF N PF complexes of cobalt (2,3,4,5) and nickel (6). This paper summarizes our more recent results in this area with particular emphasis on binuclear complexes of chromium, molybdenum, and tungsten as well as some new results on iron carbonyl derivatives. 

In contrast to the chalcogen-bridged complexes, no similar oxygen-bridged compounds of iron, cobalt, or nickel exist. However, we obtained such oxo or i-ol-carbonyl complexes of chromium and its homologs, as well as of rhenium. The compounds are the products of the reactions of the respective metal carbonyls with bases (VII). 

Consequently, the elements to the left of the noble metals show strongest (ft)-character in their zero-valent oxidation state. Thus iron(O), cobalt(O) and nickel(O) are typically (b), forming inter alia strong carbonyl complexes, while the higher oxidation states of these elements have no marked ( )-character at all. Elements in zero-valent state in fact display (b) -character as far left in the periodic system as chromium, or even vanadium, which in higher oxidation states behave as very typical (a)-acceptors. To the right of the noble metals, on the other hand, the metals in their zero-valent states do not show any marked (6)-character they do not form e.g. carbonyl or olefin complexes. 

The number of complexes of this type is considerably higher than for inclusion-and carbonyl complexes, because the components of the complexes can be varied much more Substituted cyclophanes from [22]- up to [26]cyclophanes, as well as indenophanes are used as ligands for metal fragments, which may consist of chromium, iron, ruthenium, rhodium, iridium or cobalt as metal units, and Cp-, Cp - and C R -units as stabilizing co-ligands. From Fig. 21 the importance of the oxidation state and position in the periodic table of the individual metals can be seen [48a] cobalt-III forms monocomplexes only, whereas the lower sited iridium-IIl also forms the biscomplexes for cobalt. 

Chiral salen chromium and cobalt complexes have been shown by Jacobsen et al. to catalyze an enantioselective cycloaddition reaction of carbonyl compounds with dienes [22]. The cycloaddition reaction of different aldehydes 1 containing aromatic, aliphatic, and conjugated substituents with Danishefsky s diene 2a catalyzed by the chiral salen-chromium(III) complexes 14a,b proceeds in up to 98% yield and with moderate to high ee (Scheme 4.14). It was found that the presence of oven-dried powdered 4 A molecular sieves led to increased yield and enantioselectivity. The lowest ee (62% ee, catalyst 14b) was obtained for hexanal and the highest (93% ee, catalyst 14a) was obtained for cyclohexyl aldehyde. The mechanism of the cycloaddition reaction was investigated in terms of a traditional cycloaddition, or formation of the cycloaddition product via a Mukaiyama aldol-reaction path. In the presence of the chiral salen-chromium(III) catalyst system NMR spectroscopy of the crude reaction mixture of the reaction of benzaldehyde with Danishefsky s diene revealed the exclusive presence of the cycloaddition-pathway product. The Mukaiyama aldol condensation product was prepared independently and subjected to the conditions of the chiral salen-chromium(III)-catalyzed reactions. No detectable cycloaddition product could be observed. These results point towards a [2-i-4]-cydoaddition mechanism. 

Many carbonyl and carbonyl metallate complexes of the second and third row, in low oxidation states, are basic in nature and, for this reason, adequate intermediates for the formation of metal— metal bonds of a donor-acceptor nature. Furthermore, the structural similarity and isolobal relationship between the proton and group 11 cations has lead to the synthesis of a high number of cluster complexes with silver—metal bonds.1534"1535 Thus, silver(I) binds to ruthenium,15 1556 osmium,1557-1560 rhodium,1561,1562 iron,1563-1572 cobalt,1573 chromium, molybdenum, or tungsten,1574-1576 rhe-nium, niobium or tantalum, or nickel. Some examples are shown in Figure 17. 

Under the same conditions, cobalt acetylacetonate afforded a mixture of four products the mono-, di-, and triacetylated chelates (XVII, XVIII, and XIX), along with the starting material. In contrast to the chromium chelates, the mixture of cobalt complexes was cleanly separated by chromatography. The identity of each of these products was established by an NMR spectrum. The presence of uncoordinated carbonyl groups was revealed by infrared absorption at 1675 cm.-1... 

FT-ICR, see Fourier-transform ion cyclotron resonance Fullerene[60], germanium-germanium addition, 10, 748 Fullerenes with cobalt, 7, 51 on cobalt Cp rings, 7, 73 inside metallodendrimers, 12, 401 microwave applications, 1, 334 Pd rc-complexes, 8, 348 Ru—Os complexes, 6, 830 with tungsten carbonyls, 5, 687 )2-Fullerenes, with platinum, 8, 634 Fulvalene actinide complex, synthesis, 4, 232 Fulvalene chromium carbonyls, synthesis and characteristics, 5, 264... 

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