Cyclopentadienyl complexes application

Bis(cyclopentadienyl) complexes are central to the organometallic chemistry of the early transition metals and feature in applications such as alkene polymerization chemistry. Parallels can be drawn between a porphyrin ligand and two cyclopentadienyl ligands, in that they both contribute a 2— formal charge and exert a considerable steric influence on other ligands in the same molecule. Several of the metalloporphyrin complexes discussed below have bis(cyclopentadienyl) counterparts, and authors in some ca.ses have drawn quite detailed comparisons, although these discussions will not be repeated here. 

Despite a common perception that organometallic chemistry essentially belongs in the province of catalysis rather than in vivo applications because of high reactivity of metal carbon bonds, certain organometallic species have very high kinetic stability. Indeed, this point is highlighted by the present wide application of the isonitrile complex Tc(ses-tamibi), [Tc(2-methoxyisobutylisonitrile)6]+, in myocardial imaging. Rhenium tricarbonyl and cyclopentadienyl complexes offer further ex-... 

The phosphorus atom in a r-coordinated phospholyl ligand still exhibits a lone-pair of electrons that is capable of binding a second metal atom, so that a phospholyl complex such as phosphaferrocene is—in contrast to ferrocene—itself a ligand. This special property which has no direct correspondence in the chemistry of cyclopentadienyl complexes has recently been fruitfully exploited as the underlying principle which allowed the introduction of phosphaferrocenes as effective ligands in catalytic applications [10, 13, 14]. 

Bis(cyclopentadienyl)vanadium(II) complexes applications, 5, 39 coordination compounds, 5, 37 vanadocenes, 5, 36... 

Manganese carbenes, preparation, 5, 825 Manganese carbonyl complexes with 776-arene complexes, 5, 787 cyclopentadienyl complexes, 5, 783 with hydrocarbon ligands, complexes, 5, 776 synthesis and characteristics, 5, 761 Manganese carbonyl halides, applications and reactivity,... 

Gillespie, A.M. and White, D.P. (2001) Understanding the steric control of stereoselective olefin binding in cyclopentadienyl complexes of rhenium an application of de novo ligand design. Organometallics, 20, 5149. 

The Diels-Alder reaction is one of the most fundamental means of preparing cyclic compounds. Since discovery of the accelerating effect of Lewis acids on the Diels-Alder reaction of a,)3-unsaturated carbonyl compounds [341-344], its broad and fine application under mild reaction conditions has been amplified. Equations (140) [341] and (141) [345], respectively, illustrate typical dramatic effects from an early reaction and from one reported more recently. Lewis acid-promoted Diels-Alder reactions have been reviewed [7,8,346-353]. In addition to the acceleration of the reaction, other important feature is its alteration of chemo-, regio-, and diastereoselectivity this will be discussed below. The titanium compounds used in Diels-Alder reaction are titanium halides (TiX4), alkoxides (Ti(OR)4), or their mixed salts (TiX (OR)4 n = 1-3). A cyclopentadienyl complex such as Cp2Ti(OTf)2 is also documented as a very effective promoter of a Diels-Alder reaction [354], In addition to these titanium salts, a few compounds such as those in Eq. (142) [355] have recently been reported to effect the Diels-Alder reaction. The third, [(/-PrO)2Ti(bpy)(OTf)(i-PrOH)] (OTf), was estimated to be a more active catalyst than Cp2Ti(OTf)2. 

Ferrocene, Fe(Ti5-C5H5)2, and related cyclopentadienyl complexes of transition metals in fact are far more thermally stable, less reactive substances than ionic cyclopentadienides, and have an extensive derivative chemistry that is typically aromatic in that their C-H bonds can undergo such electrophilic substitution reactions as Friedel-Crafts alkylation or acylation, nitration, and so on. Moreover, as a substituent, the ferrocenyl group (ri -f sl l5)Fc(ri -( 5l I4) (=R) is even more effective than a phenyl substituent in stabilizing carbenium ions [RCH2]+. The redox and photochemical properties of many metaUocenyl residues make them versatile substituents with many chemical and materials applications. ... 

Bernard J, Ortner K, Spingler B, Pietzsch HJ, Alberto R (2003) Aqueous synthesis of derivatized cyclopentadienyl complexes of technetium and rhenium directed toward radiopharmaceutical application. Inorg Chem 42 1014-1022... 

Cyclopentadienyl complexes of molybdenum have also been used in asymmetric synthesis, mainly for the addition of allyl groups to carbonyl compounds (Section D. 1.3.3.3.). The chiral ligand was prepared from (—)-menthone via menthyl tosylate (see Section 3.5.1. for the alcohol)49 and introduced in an allylmolybdenum complex to give 1950. For an early review on catalytic applications of such compounds, see ref 51. 

In comparison to related AAfunctionalized cyclopentadienyl complexes, where catalytic applications of such species have been remarkably successful (especially in olefin polymerization), the use of O-functionalized compounds in catalysis still seems underdeveloped. However, the patent literature is rapidly growing in this area, which reflects the great potential for such applications that has been realized in industry and academia alike. 

In addition to the release of carbon monoxide, transition metal carbonyl complexes have also found applications in anticancer chemotherapy [212], radiolabelling [213-216], and as photosensitisers. The cobalt complex shown in Fig. 14 a demonstrates a higher anticancer activity than cis-platin in certain mammary tiunor cells Hnes [217,218]. Complexes such as Tc-99m(I)(CO)3(OH2)3 along with hydroxymethyl phosphine derivatives [219] and the cyclopentadienyl complex shown in Fig. 14b have useful radiopharmaceutical applications, in diagnosis, using Tc, as the metal centre, and in therapy based on Re and Re isotopes [220]. 

The application of mass spectroscopy for the characterization of metal 7r-complexes is becoming increasingly popular. This section deals with the mass spectral data of several 7i-cyclopentadienyl, 7r-arene, and olefin metal 7r-complexes. Extensive studies have been made on Tu-cyclopentadienyl complexes, but little work has been done on the correlation of the mass spectral cracking patterns and energies of 7r-arene and 7r-allyl metal complexes. 

Two commonly used synthetic methodologies for the synthesis of transition metal complexes with substituted cyclopentadienyl ligands are important. One is based on the functionalization at the ring periphery of Cp or Cp metal complexes and the other consists of the classical reaction of a suitable substituted cyclopentadienyl anion equivalent and a transition metal halide or carbonyl complex. However, a third strategy of creating a specifically substituted cyclopentadienyl ligand from smaller carbon units such as alkylidynes and alkynes within the coordination sphere is emerging and will probably find wider application [22]. 

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