Cobalt complexes with ruthenium

Several complexes with cobalt in the unusually high oxidation state of (-(- 4) were reported (198,202,280) in 1974. All of the complexes reported were prepared by reaction of [Codlidtcls] with BF3 or Et20BF3 in the presence of air. The complexes were formulated (202, 280) as [Co(R2dtc)3]BF4 (R = Me, Et, Pr, or cyclohexyl), but Hendrickson and Martin (198) suggested that dimeric [Co2(R2dtc)5]BF4 (Rj = Me2, Et2 pyrrolidyl, MeBu", or Bzj), Co(III) complexes, form that are analogous with the ruthenium(III) complex discussed earlier. 

Cycloheptene complexes with gold, 12 348 Cyclohexadiene complexes with cobalt, 12 286 with group VIB metals, 12 225-227 with group VIIB metals, 12 240, 241 with iron, 12 264 with palladium, 12 313 with ruthenium, 12 278 with silver, 12 340... 

Nonsteroidal antiinflammatory drugs, interaction with lithium, 36 66 No-phonon transition, 35 324 Norbomadiene complexes with cobalt, 12 286 with copper, 12 328, 330, 331 with gold, 12 348, 349 with group VIB metals, 12 231 with group VnB metals, 12 241 with iron, 12 265 with palladium, 12 314 with platinum, 12 319 with rhodium, 12 300-302 with ruthenium, 12 278, 279 with silver, 12 340-342, 344, 346 Norbomylsiloxane, 42 226, 228 Notch receptor proteins, 46 473, 475 h (N)" oxime complexes, osmium, 37 260 h (N,0) oxime complexes, osmium, 37 260 (NPr ljiFeCfrdto),], magnetization versus temperature, 43 230... 

Cobalt, Nickel, and Ruthenium Complexes with Reduced Symmetry 35... 

Kinetics of aquation of [Ru(LLLL)X2], with LLLL = cyclam, 2,3,2-tet, en2, or (NH3)4, and X = Cl or Br, have been followed by cyclic voltammetry. Rate constants, and activation parameters (A// and A5 ) have been evaluated, and compared with kinetic parameters for reactions of analogous compounds of ruthenium(III) and cobalt(III). Similar trends obtain for all three sets of complexes. There is retention of stereochemistry, rates decrease as the extent of chelation in LLLL increases, and trans complexes are less labile than cis analogs. Reactivities are determined by solvation of the initial and transition states, by nephelauxetic effects, and by a-trans effects. A limiting dissociative (D) mechanism is proposed for the ruthenium complexes, with square-pyramidal geometry for the transient intermediate [cf. rhodium(III) photochemistry below. Section 5.8.10]. Differences in isomer lability have also been described for... 

Cj Hydroformation of CO with high-molecular weight olefins on either a cobalt or ruthenium complex bound to polymers. 

Although the actual reaction mechanism of hydrosilation is not very clear, it is very well established that the important variables include the catalyst type and concentration, structure of the olefinic compound, reaction temperature and the solvent. used 1,4, J). Chloroplatinic acid (H2PtCl6 6 H20) is the most frequently used catalyst, usually in the form of a solution in isopropyl alcohol mixed with a polar solvent, such as diglyme or tetrahydrofuran S2). Other catalysts include rhodium, palladium, ruthenium, nickel and cobalt complexes as well as various organic peroxides, UV and y radiation. The efficiency of the catalyst used usually depends on many factors, including ligands on the platinum, the type and nature of the silane (or siloxane) and the olefinic compound used. For example in the chloroplatinic acid catalyzed hydrosilation of olefinic compounds, the reactivity is often observed to be proportional to the electron density on the alkene. Steric hindrance usually decreases the rate of... 

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. 

The systems that we investigated in collaboration with others involved intermolecular and intramolecular electron-transfer reactions between ruthenium complexes and cytochrome c. We also studied a series of intermolecular reactions between chelated cobalt complexes and cytochrome c. A variety of high-pressure experimental techniques, including stopped-flow, flash-photolysis, pulse-radiolysis, and voltammetry, were employed in these investigations. As the following presentation shows, a remarkably good agreement was found between the volume data obtained with the aid of these different techniques, which clearly demonstrates the complementarity of these methods for the study of electron-transfer processes. 

The preparation of cyclopropanes by intermolecular cyclopropanation with acceptor-substituted carbene complexes is one of the most important C-C-bond-forming reactions. Several reviews [995,1072-1074,1076,1077,1081] and monographs have appeared. In recent decades chemists have focused on stereoselective intermolecular cyclopropanations, and several useful catalyst have been developed for this purpose. Complexes which catalyze intermolecular cyclopropanations with high enantiose-lectivity include copper complexes [1025,1026,1028,1029,1031,1373,1398-1400], cobalt complexes [1033-1035], ruthenium porphyrin complexes [1041,1042,1230], C2-symmetric ruthenium complexes [948,1044,1045], and different types of rhodium complexes [955,998,999,1002-1004,1010,1062,1353,1401-1405], Particularly efficient catalysts for intermolecular cyclopropanation are C2-symmetric cop-per(I) complexes, as those shown in Figure 4.20. These complexes enable the formation of enantiomerically enriched cyclopropanes with enantiomeric excesses greater than 99%. Illustrative examples of intermolecular cyclopropanations are listed in Table 4.24. 

In 1989, a method for the peroxysilylation of alkenes nsing triethylsUane and oxygen was reported by Isayama and Mnkaiyama (eqnation 25). The reaction was catalyzed by several cobalt(II)-diketonato complexes. With the best catalyst Co(modp)2 [bis(l-morpholinocarbamoyl-4,4-dunethyl-l,3-pentanedionato)cobalt(n)] prodnct yields ranged between 75 and 99%. DiaUcyl peroxides can also be obtained starting from tertiary amines 87, amides 89 or lactams via selective oxidation in the a-position of the Af-fnnctional group with tert-butyl hydroperoxide in the presence of a ruthenium catalyst as presented by Murahashi and coworkers in 1988 ° (Scheme 38). With tertiary amines 87 as substrates the yields of the dialkyl peroxide products 88 ranged between 65 and 96%, while the amides 89 depicted in Scheme 38 are converted to the corresponding peroxides 90 in yields of 87% (R = Me) and 77% (R = Ph). 

Careful studies by Doyle et al. (163) have also shown that soluble ruthenium species are inactive for hydrocarbon formation. A soluble system could be maintained in heptane solvent at 250°C under 100 atm of 1 1 H2/CO for many hours by taking precautions to avoid the possible introduction of impurities into the system and by slowly raising the temperature. No hydrocarbon formation was observed in this reaction. Only upon heating to about 260°C was the disappearance of soluble ruthenium complexes noted, along with the formation of linear alkanes. These results may suggest that metastable homogeneous ruthenium solutions can be formed, as has been reported for cobalt complexes (56) precipitation of the metal may be an autocatalytic process. 

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