Metallocenes substituents

Metallocene derivatives may be named either by the standard organic suffix (functional) nomenclature or by prefix nomenclature. The organic functional suffix system is described in Section P-33 of Ref. 3. Metallocene substituent group names have endings ocenyl , ocenediyl , ocenetriyl , etc. 

Schmidt, E.Yu., N.V. Zorina, M.Yu. Dvorko et al. 2011. A general synthetic strategy for the design of new BODIPY fluorophores based on pyrroles with polycondensed aromatic and metallocene substituents. Chem EurJ 17 3069-3073. 

Bent ansa-metallocenes of early transition metals (especially Ti, Zr, Hf) have attracted considerable interest due to their catalytic activity in the polymerization of a-olefins. Ruthenium-catalyzed olefin metathesis has been used to connect two Cp substituents coordinated to the same metal [120c, 121a] by RCM or to connect two bent metallocenes by cross metathesis [121b]. A remarkable influence of the catalyst on E/Z selectivity was described for the latter case while first-generation catalyst 9 yields a 1 1 mixture of E- and Z-dimer 127, -127 is the only product formed with 56d (Eq. 19). 

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... 

At present, the difficulties described in 7-9 can be solved. The use of MAO can be avoided by the use of non-MAO catalysts such as cationic Group 4 metallocenes or neutral Group 3 metallocenes. It has been found that the molecular weight of the resulting polymer can be increased by introducing substituents at the 2,5-position in the cyclopentadienyl group of the... 

The exchange of zirconium in isostructural complexes leads to a new family of asymmetric metallocenes (Fig. 1) bearing a 2-methyl substituent and varied substituents in positions 5, 6, and 7 of the indenyl moiety. After borate activation all catalysts show an unexpected high and constant activity toward the polymerization of propylene and lead to significantly increased molecular weight products compared to the zirconocene species [9-11],... 

By using different Cp ligands (Cp, Cp, ebthi), additional ligands (THF, pyridine, acetone), and metals (Ti, Zr), a fine-tuning of the reactions of these complexes has been feasible. Additional influences are exerted by, e. g., the substituents on the substrate, the stoichiometry used, the solvents, and other reaction conditions. Complexes of this type have also been prepared and used in connection with a multitude of substrates, and in many cases the products differ markedly from those obtained with conventional metallocene sources. 

Various phenyl-substituted ketimines and aldimines react with metallocenes 1 and 2, in a manner that depends on the substituents present [41]. In all cases, elimination of the al-kyne is observed. Complex 2b reacts with PhN=CMePh to give the r 2-complex 64, which is stabilized by an additional pyridine ligand [41a], In the reactions of 1 or 2a with the ketimine HN=CPh2, hydrogen transfer generates complexes 65. Two molecules of the aldimine PhN=CHPh are coupled by 2a to give the cyclic diamido complex 66 [41b]. 

Methyl substituents, in chiral metallocene catalysts, 16 106 v-Methyl substituents, in chiral metallocene catalysts, 16 106 Methyl tert-amyl ether (TAME), 12 404-405... 

Since 1987 numerous metallocenes, in particular ferrocenes, have been found to possess NLO properties, many of which have substituents containing polyene conjugate groups,72 Scheme 14. 

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