Cyclopentadiene, derivatives cyclopentadienyl metal complexes

The strategies used to synthesize metal complexes with the cyclopentadienyl ligands portrayed in Scheme 13 are briefly described below. The most widely used procedure begins with the corresponding cyclopentadiene derivative, which can be transformed into a cyclopentadienyl metal complex by a variety of metallation methods as described in... 

Unlike the compounds obtained with the heavier halogens, polyfluori-nated metallocene derivatives cannot be prepared from the permercurated metallocenes. Thermally stable pentafluorinated ruthenocenes have been made from the (oxocyclohexadienyl)(cyclopentadienyl)metal complexes by flash vacuum pyrolysis (Scheme 6).53 54 Decafluorometallocenes, [M(C5F5)2], are still unknown potential routes to these compounds starting from fluorinated cyclopentadiene (C5F5H)55 or from the decachlorometal-locenes48 have been unsuccessful. However, there seems to be no fundamental steric or electronic barrier to their eventual preparation. 

This review deals with metal-hydrocarbon complexes under the following headings (1) the nature of the metal-olefin and -acetylene bond (2) olefin complexes (3) acetylene complexes (4) rr-allylic complexes and (5) complexes in which the ligand is not the original olefin or acetylene, but a molecule produced from it during complex formation. ir-Cyclopentadienyl complexes, formed by reaction of cyclopentadiene or its derivatives with metal salts or carbonyls (78, 217), are not discussed in this review, neither are complexes derived from aromatic systems, e.g., benzene, the cyclo-pentadienyl anion, and the cycloheptatrienyl cation (74, 78, 217), and from acetylides (169, 170), which have been reviewed elsewhere. 

In a first approximation supra-Cp metal complexes can be prepared the same way as normal or other Cp-metal and organo-metal bonds in general. The methods used most often (see Appendix) are the metathesis reaction [Eq. (1)] followed in number by oxidative additions (Eq. (2)] and metallation/deprotonation reactions [Eq. (3)]. The latter is especially important for the cyclpentadienyl alkali metal compounds. A useful variation of reaction (3) is the formation of CpTl in an acid/base reaction from cyclopentadiene and thallium ethoxide [Eq. (3b)]. This represents a convenient route to cyclopentadienylthallium compounds, which are also valued (in place of Cp alkalis) as mild Cp-transfer reagents for the synthesis of difficultly isolable cyclopentadienyl derivatives (77). 

Roesky introduced bis(iminophosphorano)methanides to rare earth chemistry with a comprehensive study of trivalent rare earth bis(imino-phosphorano)methanide dichlorides by the synthesis of samarium (51), dysprosium (52), erbium (53), ytterbium (54), lutetium (55), and yttrium (56) derivatives.37 Complexes 51-56 were prepared from the corresponding anhydrous rare earth trichlorides and 7 in THF and 51 and 56 were further derivatised with two equivalents of potassium diphenylamide to produce 57 and 58, respectively.37 Additionally, treatment of 51, 53, and 56 with two equivalents of sodium cyclopentadienyl resulted in the formation of the bis(cyclopentadienly) derivatives 59-61.38 In 51-61 a metal-methanide bond was observed in the solid state, and for 56 this was shown to persist in solution by 13C NMR spectroscopy (8Ch 17.6 ppm, JYc = 3.6 2/py = 89.1 Hz). However, for 61 the NMR data suggested the yttrium-carbon bond was lost in solution. DFT calculations supported the presence of an yttrium-methanide contact in 56 with a calculated shared electron number (SEN) of 0.40 for the yttrium-carbon bond in a monomeric gas phase model of 56 for comparison, the yttrium-nitrogen bond SEN was calculated to be 0.41. 

For the analogous cyclopentadiene(5ee Cyclopentadienyl) derivative, prepared by a different route, the complex is unstable in solution and is believed to dissociate back to H2 and the Mo-Mo triple-bonded complex. In view of the fact that many catalytic cycles utilize hydrogen, these types of complexes are important models. Interactions of dihydrogen leading to cleavage of the metal-metal bond are discussed in Section 7.1.4. 

Endocyclic dienes ranging in ring size from four to seven have also been used in the intramolecular Diels-Alder reaction. Cyclobutadienes are prepared from the corresponding metal complexes [37]. Cyclopentadienes are most readily prepared by alkylation of cyclopentadienyl anion [38, 39]. They are also available by Michael addition to fulvene derivatives and by aminal exchange [40, 41]. 

Cyclopentadiene (1), a simple organic compound first found in the volatile parts of coal tar, has become one of the most important ligands used in organometallic chemistry. More than 80% of all known organometallic complexes of the transition metals contain the cyclopentadienyl fragment or a derivative thereof. 

Bis(cyclopentadienyl)iron derivatives, ferrocenes, are remarkably stable against heat and air and undergo various kinds of chemical reactions. They are usually prepared by the reaction of FeCh with an alkali metal salt of cyclopentadienyl or cyclopentadiene in the presence of base [51]. Although ferrocene derivatives basically have chemical reactivities similar to those of aromatic compounds, they have found only limited applications to organic synthesis so far. However, because chiral ferrocenylphosphines are capable of having both planar chirality and an asymmetry in the side chain in their rigid framework, they have been used recently in a number of asymmetric reactions. In this section, synthesis and developments of monocyclopentadienyl complexes and ferrocenylphosphines are described. The general chemistry of ferrocenes and half metallocene complexes is reviewed elsewhere [52-53]. 

Ligand-substitution reactions (or nucleophilic attack at the metal) in cyclopentadienyl complexes of palladium have been used to prepare new derivatives. The classical introduction of a cyclopentadienyl moiety by use of TlCp or NaCp and a cationic or halo palladium complex has been employed in the synthesis of complexes [Pd( 7 -Cp)(dppe)]Tf " and PdCp 3-(CHO)C6H3C(H)=NCy. A novel route has been applied that involves deprotonation of cyclopentadiene by a coordinated hydroxyl group to afford the cyclopentadienyl complexes shown in Equation (63). ... 

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