Half-Sandwich Derivatives

HALF-SANDWICH DERIVATIVES WITH ACYLPYRAZOLONE LIGANDS... 

Most of the compounds synthesized are lanthanide(III) COT and substituted COT derivatives. In particular, a wide variety of half sandwich derivatives containing Ln to halide, chalcogenide, pnicogenide and hydrocarbyl bonds are known. A general approach to ionic lanthanocene derivatives is ... 

Although the chemistry of zirconium in its lower oxidation states is still relatively unexplored, it is developing. Examples which offer the possibility of further exploitation include the blue, paramagnetic zirconium(III) compound 32) [L2Zr(/r-Cl)2ZrL2] L = C5H3(SiMe3)2-l,3, and the sandwich and half-sandwich compounds derived from cycloheptatriene red... 

The half-sandwich and sandwich complexes of phospholides and phosphole tetramer are known even for the nontransition metals. The half-sandwich arrangement was studied for lithium tetramethylphospholide [89AG(E)1367] and sodium derivative 127 generated from the phospholide tetramer and sodium in the presence of 1,2-dimethoxyethane [94JA3306 96AG(E)1125]. Potassium and 1,2-dimethoxyethane in THE in these conditions give a full dianionic sandwich 128. 

Dihydro-lH-l,2-azaboroles derive from cyclopentadiene by the isoelectronic replacement of a C=C group by a BN moiety ". The neutral rings react in xs boiling Fe(CO)j without any other solvent to form red-brown iron-dihydro-1,2-azaborolyldi-carbonyl dimers as their cis and transisomers in 56% yield, or with CojfCOg in petroleum ether at 60-80°C to the half-sandwich complex (dihydro-1,2-azaborolyl)Co(CO)2 (40%). The CO group can easily be substituted by olefins ... 

In contrast to the chemistry of the zinc complexes [TpRR]ZnR, the cadmium alkyl derivatives have not been used to prepare an extensive series of half-sandwich [TpRR]CdX complexes. However, several [Tp JCdX complexes supported by sterically demanding tris(pyrazolyl)hydroborato ligands, e.g., [TpBut]CdCl (98), [TpBut]CdI (91), [Tp lCdl (91), and [TpBut,Me]Cd(Tj2-02N0) (91), have been synthesized by metathesis between CdX2 and either K[TpRR ] or Tl[TpRR ] [Eq. (15)]. 

Boehm et al.100 have synthesised and studied a series of half-sandwich rhodium (III) and iridium (III) complexes, derivatives of salicylaldehyde and L-amino acid esters. The diastereoselectivity has shown strong dependence on the type of metal as well as amino acid residue. The labile configuration of the metal atoms was suggested because of changes in the diastereomers ratio with increasing temperature. Fast epimerisation at the metal atom was suggested for some S-phenylalanine complexes. 

Silane a-complexes of the Group 6 metals are among the best studied. Three families of compounds are particularly noteworthy. These are the half-sandwich arene complexes [Cr(ri -HSiMe2H)(CO)2(C6Me6)] (27), the above-mentioned Kubas s complexes and the pentacarbonyl derivatives [M(t -HSiR3)(CO)5]. ... 

Several half-sandwich-type derivatives, in which the allenylidene unit is generated from propargylic alcohols following the Selegue s protocol, are known. Representative examples include (1) the cationic cyclopentadienyl complexes [CpOs (=C=C=CPh2)(L )(L )][PF6] (L = = PPhs, Pi-Prs = Pi-Prs, = CO,... 

In accord with the expected trans influence of the 71-acceptor aUenylidene unit [212], substitution of the chloride ligand by different anionic nucleophiles in complexes frans-[MCl(=C=C=CR R )(Pi-Pr3)2] (M = Rh, Ir) is favored, affording new aUenylidene derivatives frans-[MX(=C=C=CR R )(P/-Pr3)2] (X = I, F, OH, N3, etc.) (see reactivity studies below). Of particular interest is the behavior of the Rh(I) species frans-[RhCl(=C=C=CPh2)L2] (L = Pf-Pr3, f-Pr2AsCH2CH20Me) towards NaCsHs since the reactions lead to the clean formation of complexes 40 (Scheme 13), the only half-sandwich-type Group 9 allenylidenes presently known [206, 209]. 

The conformational orientation adopted by the allenylidene group =C=C= CR R also merits comment. Thus, in half-sandwich complexes, mainly derived from [M(77 -CxHy)L2] (M = Fe, Ru, Os) metal fragments, a marked preference of the allenylidene group to adopt a vertical orientation in which the ipso carbon atoms of the R /R substituents are contained in the molecular plane (pseudo mirror plane bisecting the half-sandwich metal fragment) is observed. Preference for this conformation arises from the dominant metal ( xy-Cp back donation of the metal-HOMO into the allenylidene-LUMO n orbital (see Fig. 13). In contrast to this general trend, an unusual horizontal orientation of the allenylidene group was... 

Zirconocene and Half-Sandwich Zirconium Derivatives The development of a single-site heterogeneous catalyst for metallocene-based polymerization catalysis has also been explored extensively with zirconocene and half-sandwich zirconium derivatives [32, 75, 91, 92]. 

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