It acceptor ligands

In the mixed case—one ir-donor and a it-acceptor ligand, as in OsHCl(CO) (P1 Pr3)2—the structure III of Scheme 1 (in which the -ir-donor X ligand and the tt-acceptor A ligand are trans to each other) is more stable.22 In a T structure, which... 

C. Rong, M. T. Pope, lacunary polyoxometalate anions are It-acceptor ligands-Characterization of some tungstoruthenate (II, III, IV, V) heteropolyanions and their atoms-transfer reactivity, J. Am. Chem. Soc. 114 2932 (1992). 

Orientational Preferences for it-Acceptor Ligands such as Ethylene.95... 

Low oxidation states have also dominated the previous discussion because they favor binding soft, it-acceptor ligands (CO, C2H4, etc.) that are most typical of organometallic chemistry. If we avoid these ligands and restrict the coordination sphere to alkyl, aryl, H, and Cp, however, high oxidation states appear in the resulting compounds. We look at... 

Stabilization of /j -alkyl and -aryl derivatives of transition metals can be enhanced by the judicious inclusion of various other stabilizing ligands in the complex, even though such ligands are known not to be an essential prerequisite. Particularly efficacious are potential IT acceptors (see below) such as AsPh3, PPh3,... 

The effect of the CFSE is expected to be even more marked in the case of the heavier elements because for them the crystal field splittings are much greater. As a result the +3 state is the most important one for both Rh and Ir and [M(H20)6] are the only simple aquo ions formed by these elements. With rr-acceptor ligands the +1 oxidation state is also well known for Rh and Ir. It is noticeable, however, that the similarity of these two heavier elements is less than is the case earlier in the transition series and, although rhodium resembles iridium more than cobalt, nevertheless there are significant differences. One example is provided by the +4 oxidation state which occurs to an appreciable extent in iridium but not in rhodium. (The ease with which Ir, Ir sometimes occurs... 

The structures of several adducts can be rationalized on the basis [128] that in a 5-coordinate low-spin d8 tbp system, the acceptor ligands prefer to occupy an equatorial site (IrCl(CO)2(PPh3)2) whereas a 7r-donor prefers an axial site. In a square pyramidal situation, it is weakly bonded acceptors that prefer the apical position, e.g. (IrCl(S02)(C0)(PPh3)2. 

Schrock-type carbenes are nucleophilic alkylidene complexes formed by coordination of strong donor ligands such as alkyl or cyclopentadienyl with no 7T-acceptor ligand to metals in high oxidation states. The nucleophilic carbene complexes show Wittig s ylide-type reactivity and it has been discussed whether the structures may be considered as ylides. A tantalum Schrock-type carbene complex was synthesized by deprotonation of a metal alkyl group [38] (Scheme 7). 

Nearly all the presently known compounds contain one or more w-acceptor ligands (e.g., CO, Cp, RjP) on the transition metal. These ligands may, as has classically been assumed for alkyls (72), dissipate some of the negative charge density on the central metal. However, it will be stressed later (Section IV) that such stabilizing ligands are unnecessary, and their role may in any case be more complex. 

Perhaps the most important chemical property of these complexes is their potential as catalysts, particularly of the early transition metal isoleptic compounds for a-olefin polymerization. This arises because unlike the methyls, they are sufficiently stable to be used at temperatures where polymerization rates are adequate. Some data are summarized in Table VIII ( 9) TT-acceptor ligands are clearly disadvantageous. It will be seen that some of the systems are more active than Ziegler types, although stereoselectivity is poorer. 

Additional combinatorial variation sites allow the heterocyclic self-assembly units. Thus, it has been shown that heterocycles 11 and 14-17 can serve as A-analogous donor-acceptor ligands self-assembling with the T-analogous acceptor-donor ligands isoquinolone 12 and 7-azaindole 18 (Scheme 30) [92]. All combinations form the heterobidentate ligands exclusively upon simple mixing in the presence of a transition metal salt (proven by X-ray, NMR). 

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