Ligands addition with

Asymmetric addition of phosphonate [RCH2PO(OEt)2] to 4-substituted cyclohexanones has been promoted by chiral ligand additives with preferential formation of the Z-diastereoisomer in high enantiomeric excess. ... 

In addition to halopeiidol, the putative neuroleptics, limcazole (311), lemoxipiide (312), and gevotioline (313) bind to (7-ieceptois as does the dopamine uptake blocker, GBR 12909 (314) and two ligands active at the NMDA receptor, ifenprodil (315) and CNS 1102 (316). NPC 16377, (317) is a selective (7-teceptor ligand. MAO inhibitors and antidepressants also bind to (7-teceptors. Some evidence indicates that (7-teceptors in the brain are in fact a form of cytochrome which may account for the diversity of ligands interacting with (7-sites. 

In titanium acylates, the carboxylate ligands are unidentate, not bidentate, as shown by ir studies (333,334). The ligands are generally prepared from the hahde and silver acylate (335). The ben2oate is available also from a curious oxidative addition with ben2oyl peroxide (335—338) ... 

The catalytic cycle (Fig. 5) (20) is well estabUshed, although the details of the conversion of the intermediate CH COI and methanol into the product are not well understood the mechanism is not shown for this part of the cycle, but it probably involves rhodium in a catalytic role. The CH I works as a cocatalyst or promoter because it undergoes an oxidative addition with [Rh(CO)2l2]% and the resulting product has the CO ligand bonded cis to the CH ligand these two ligands are then poised for an insertion reaction. 

The 3,5-bis(trifluoromethyl)pyrazolate analog [Ir(cod)(/x-3,5-(CF3)2pz)]2 does not enter into oxidative addition with iodine, methyl iodide, or acetylenes. The mixture of pyrazolate and 3,5-bis(trifluoromethyl)pyrazolate gives [(rj -codllrf/x-pz)(/L-3,5-(CF3)2pz)Ir(rj -cod)], which reacts with bis(trifluoromethyl)acetylene in a peculiar manner [83JCS(CC)580], producing 145, where 3,5-bis(trifluoromethyl) pyrazolate is replaced by the ethylene bridge and the rj -coordination mode of one of the cod ligands is converted into the rj -allylic mode. 

These are generally analogous to those of Wilkinson s compound, with the important difference that ligand dissociation cannot occur, so that the product of oxidative addition with H2 cannot have a vacant site to bind an alkene and will thus not act as a hydrogenation catalyst [53]. 

Mo(NO)2L2Cl2, from isocyanide ligand addition to [Mo(NO)2Cl2]. These complexes are, in general, analogous to many known complexes of these metals with other ligands. 

Careful TEM analyses (with alkane thiols) clearly showed that the big prismatic particles are indeed broken into small particles (Figure 20) upon ligand addition [32]. 

Figure 20. A TEM snapshot of large polyhedral particles prepared by the inverse micelle system being broken by the ligand addition. The ligand featured here is decanethiol. (Reprinted with permission from Ref. [32], 2005, American Chemical Society.)...

Mechanistically, the nucleophilic addition can occur either by internal ligand transfer or by external attack. Generally, softer more stable nucleophiles (e.g., malonate enolates) are believed to react by the external mechanism and give anti addition, whereas harder nucleophiles (e.g., hydroxide) are delivered by internal ligand transfer with syn stereochemistry.120... 

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