Lead, cyclopentadienyl

The full ab-initio molecular dynamics simulation revealed the insertion of ethylene into the Zr-C bond, leading to propyl formation. The dynamics simulations showed that this first step in ethylene polymerisation is extremely fast. Figure 2 shows the distance between the carbon atoms in ethylene and between an ethylene carbon and the methyl carbon, from which it follows that the insertion time is only about 170 fs. This observation suggests the absence of any significant barrier of activation at this stage of the polymerisation process, and for this catalyst. The absence or very small value of a barrier for insertion of ethylene into a bis-cyclopentadienyl titanocene or zirconocene has also been confirmed by static quantum simulations reported independently... 

Lead (bis-cyclopentadienyl) [1294-74-2] M 337.4. Purified by vacuum sublimation. Handled and stored under N2. 

Interaction of the iron metal atoms with thiophenes (thiophene, 2-methyl-, and 2,5-dimethylthiophene) in the vapor phase at 77 K with subsequent heating in a carbon monoxide atmosphere also leads to the formation of ferrole 83 [76JOM(l 18)37, 77CJC3509]. The iron cyclopentadienyl ring is planar and all the bonds have multiple character. 

Reaction of the cyclopentadienyl rhodium and iridium tris(acetone) complexes with indole leads to the species 118 (M = Rh, Ir) [77JCS(D)1654 79JCS(D)1531]. None of these compounds deprotonates easily in acetone, but the iridium complex loses a proton in reaction with bases (Na2C03 in water, r-BuOK in acetone) to form the ri -indolyl complex 119. This reaction is easily reversed in the presence of small amounts of trifluoroacetic acid. 

Active Figure 15.11 Energy levels of the five cyclopentadienyl molecular orbitals. Only the six-7r-electron cyclopentadienyl anion has a filled-shell configuration leading to aromaticity. Sign in at www.thomsonedu.com to see a simulation based on this figure and to take a short quiz. 

Synthetic routes to mixed cyclopentadienyl/guanidinato complexes of Group 4 metals have also been developed. Scheme 78 illustrates two typical reactions leading to such compounds. 

Acyl chlorides react with epoxides in the presence of a Eu(dpm)3 catalyst or a YCp2Cl catalyst (where Cp is cyclopentadienyl) to give chloro esters. A related reaction with epi-sulfides leads to 2-chlorothio-esters. Aziridines have been opened with MgBr2 to give 2-haloamides in a related reaction. 

While structural evidence indicates that radical 44 is delocalized through the five carbon centers, it has been suggested that annelation of the cyclopentadienyl framework with rigid bicyclic systems leads to localized structures, as in compound 45 (Fig. 7.20). The X-ray structure of 45 indicates that the rather long distances between C1-C2 (1.445 A), C1-C5 (1.442 A), and C3-C4 (1.482 A) correspond to... 

It has been shown that boratabenzenes can provide the framework for a new family of stable, 19-electron iron-sandwich complexes. For example, treatment of (C6Me6)FeCp with MeBBr2 leads to insertion to furnish the corresponding r 6-boratabenzene adduct (Scheme 18).33 The structures, EPR spectra, and reactivity of these boratabenzene complexes are very similar to their well-studied (arene)Fe(cyclopentadienyl) precursors. The unpaired electron resides in an antibonding orbital that is largely metal based. 

Its aromaticity cannot, of course, be tested by attempted electrophilic substitution, for attack by X would merely lead to direct combination with the anion. True aromatic character (e.g. a Friedel-Crafts reaction) is, however, demonstrable in the remarkable series of extremely stable, neutral compounds obtainable from (15), and called metallocenes, e.g. ferrocene (16), in which the metal is held by n bonds in a kind of molecular sandwich between the two cyclopentadienyl structures ... 

Several tri(cyclopentadienyl)tin(ll) and lead(ll) complexes have been prepared with alkali metal cations. The arrangement of Cp rings around the metal is in a paddle wheel configuration the alkali cation is bound to Cp and not Sn or Pb, further supporting the view of a weak alkali metal group 14 bond. Representative examples of these compounds include (77S-Cp)2E(/r-Cp)-Na(PMDTA) (E = Sn 230, Pb 231).239 240... 

By a sequence of reactions, the two cyclopentadienyl rings can be connected. Using C2H5OCOCH2COCl as the starting acid chloride, it is possible to attach the acyl end to one of the C5H5 rings. Hydrolysis to remove the ethyl group and conversion of that end to an acid chloride followed by another Friedel-Crafts reaction and reduction of the product leads to... 

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