Cyclopentadienyls, ring substituted

Cyclopentadienyl rings substituted by fullerene units have been synthesized in order to obtain molecules presenting donor-acceptor interactions.The synthesis involves the [4- -2]-cycloaddition of a CoCp(C4Ph4) derivative with Cso at rather high temperatures that led to an organocobalt compound 314 stable in air but which proved to be apparently unstable under redox conditions (Equation (49)). 

Metallocene Catalysts. Polymerization of cycloolefins with Kaminsky catalysts (combinations of metallocenes and methylaluminoxane) produces polymers with a completely different stmcture. The reactions proceeds via the double-bond opening in cycloolefins and the formation of C—C bonds between adjacent rings (31,32). If the metallocene complexes contain bridged and substituted cyclopentadienyl rings, such as ethylene(hisindenyl)zirconium dichloride, the polymers are stereoregular and have the i j -diisotactic stmcture. 

The most notable chemistry of the biscylopen-tadienyls results from the aromaticity of the cyclopentadienyl rings. This is now far too extensively documented to be described in full but an outline of some of its manifestations is in Fig. 25.14. Ferrocene resists catalytic hydrogenation and does not undergo the typical reactions of conjugated dienes, such as the Diels-Alder reaction. Nor are direct nitration and halogenation possible because of oxidation to the ferricinium ion. However, Friedel-Crafts acylation as well as alkylation and metallation reactions, are readily effected. Indeed, electrophilic substitution of ferrocene occurs with such facility compared to, say, benzene (3 x 10 faster) that some explanation is called for. It has been suggested that. 

The crystal and molecular structure of the 44, 45, and C5-vinylferro-cenyl-thymidine show that the substituted cyclopentadienyl ring is essentially co-planar with the nucleobase (164). DFT calculations indicate that, irrespective of the extent of saturation in the bridging C2-unit in ethynyl-, vinyl- or ethyl-ferrocenyl-C5-thymidine, a similar amount of spin density is transferred to the nucleobase (Fig. 48). The reduction potentials for these compounds are shifted little compared to the parent ferrocenyl derivatives. 

Metallocenes with substituted cyclopentadienyl rings. Metallocenes with methylated rings were among the first heavy alkaline earth metallocenes to be structurally characterized, but many other substituents have been incorporated into bis(cyclopentadienyl) complexes. Under this classification are included compounds with indenyl ligands, which in... 

In order to synthesize substituted bis(indenyl)methanes, Nifant ev and coworkers generated several aromatic dilithiated compounds with two metalated cyclopentadienyl rings... 

Metallocenes have a transition metal sandwiched between two cyclopentadienyl rings. The cyclopentadienyl rings may not necessarily be parallel because of bridging. They may be further substituted to restrict access to the metal. The catalyst structure can be changed to make different polymeric properties. A typical example would be the zirconium metallocene shown below. 

When (40) is irradiated by Hg lamp at room temperature in the presence of pentamethyl-cyclopentadienyl dicarbonyl cobalt(III), Co(III) dithiolato complexes (45) and (46) are formed implying involvement of benzonitrile sulfide as an intermediate <92CL243). Thermolysis of (40) (and its phenyl ring substituted derivatives (40a)) at 110-140 °C in aromatic solvents results in formation of another heterocyclic mesoionic structure (47) and appears to proceed as a radical process (Scheme 2) (91TL4023). The reaction is inhibited by radical scavengers. 

The most important reactions of dicyclopentadienybron may be attributed to the aromatic behavior of cyclopentadienyl ring in the complex. Thus, the ring can undergo electrophilic substitution reactions with electrophiles to form various mono-, and disubstituted products. For example, with an equimolar of acetyl chloride and in the presence of aluminum chloride, the product is essentially monoacetylferrocene while in the presence of an excess of both of the reagents, the major product is 1,1-diacetylferrocene with a minor yield of 1,2-diacetylferrocene. 

Structural data confirm that the Daniphos ligands are readily adaptable to most ligand environments. A major advantage of the chromium system is the commercial availability of phenylethylamine and its derivatives in both enantiomeric forms. In contrast to the cyclopentadienyl ring, arenes have an almost unlimited potential for controlled substitutional variation, accessible through standard reaction protocols. 

Ring Substitution Reactions of Metal-Cyclopentadienyls and Metal-Arenes... 

We have seen how a substituent on one cyclopentadienyl ring in ferrocene markedly affects subsequent ring substitution reactions. While certain transformations of this type are at least partially determined by steric factors, it seems certain that resonance and inductive interactions also play a very important role in determining orientation. Electronic transmissions both within and across the cyclopentadienyl rings are not fully understood, since the precise nature of the bonding in ferrocene is still uncertain. 

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