Metal-ligand coordination coupling

Figure 7.3 Metal-ligand coordination coupling (non-covalent coupling) of terpyridine end-functional blocks poly A and poly B (schematic representation).

The metal-to-ligand coordination coupling chosen for the construction of a family of giant amphiphiles was that of a metal-terpyridine complex, which is known to form stable bis-complexes with a variety of transition-metal ions.275 The versatility of this metal-to-ligand system has been recently demonstrated in the construction of a series of coordination polymers and block copolymers.276... 

Experimental confirmation of the metal-nitrogen coordination of thiazole complexes was recently given by Pannell et al. (472), who studied the Cr(0), Mo(0), and W(0) pentacarbonyl complexes of thiazole (Th)M(CO)5. The infrared spectra are quite similar to those of the pyridine analogs the H-NMR resonance associated with 2- and 4-protons are sharper and possess fine structure, in contrast to the broad, featureless resonances of free thiazole ligands. This is expected since removal of electron density from nitrogen upon coordination reduces the N quad-rupole coupling constant that is responsible for the line broadening of the a protons. 

X-ray structural studies of the diamagnetic anion (406) confirm that the Ir(-I) center is in a distorted coordination geometry intermediate between square planar and tetrahedral, with the P donor atoms in a cis position. The metal-ligand bond distances do not show significant changes among (404), (405), and (406). The Ir1/0 and Ir0/(-1) redox couples are measured at easily accessible potentials and are solvent dependent. 

Combines sensitivity of EPR and high resolution of NMR to probe ligand superhyperfine interactions For paramagnetic proteins enhanced chemical shift resolution, contact and dipolar shifts, spin delocalization, magnetic coupling from temperature dependence of shifts Identification of ligands coordinated to a metal centre... 

Alternatively, the transmetalation can be facilitated by increasing the nucleophilicity of the carbon nucleophile participating in the cross-coupling, which is most often done by increasing the electron density on the metal by coordination of extra anionic ligands. Two distinct approaches to nucleophilic activation are (i) the addition of appropriate Lewis bases to the reaction mixture (nucleophilic catalysis) or (ii) the use of a preformed, electron-rich, organo-metallic reagent with enhanced nucleophilicity. 

If dendrimers contain both luminescent units and coordination sites, they can perform as luminescent ligands for metal ions [10]. Coupling luminescence with metal coordination can indeed be exploited for a variety of purposes that include investigation of dendrimer structures [11], encapsulated metal nanoparticles [12],... 

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