4,4 -Bromomethyl-2,2 -bipyridine complexes

The ruthenium complexes were attached to the specified cysteine by formation of a thioether linkage between the sulfur atom of cysteine and the methylene carbon of one of the bipyridine ligands. The reaction makes use of complexes that contain 4-bromomethyl-4 -methylbipyridine, as indicated. 

Bipyridines were synthesized by thiolatedeprotection with cesium hydroxide and reaction withhalogenides R-CH2-Br, performing the last step in Figure 13.25 with 5,5 -bis(bromomethyl)-2,2 -bipyridine and 4,4 -bis(bromobutyl)-2,2 -bipyridine. i The metal complexes depicted in Figure 13.26 were synthesized with [Ru(bipy)2Cl2], RuClj, and FeS04, respectively ... 

A new 2,2 -bipyridine-based 15-membered phosphadithiamacrocycle 150 has been synthesized by the reaction of 6,6 -bis(bromomethyl)-2,20-bipyridine and dilithium 3-phenyl-3-phosphapenta-l,5-dithiolate under high-dilution (Scheme 12.56). The phosphoryl derivative 151 was synthesized by direct oxidation of 150 at open atmosphere. The reaction of 150 and 151 with Fe(II) perchlorate gave the complexes 152 (X = lone pair, O). In both cases, a distorted octahedral environment is achieved at the Fe(II), with five sites occupied by the macrocycles 150 and 151 and the sixth by a monodentate bromine ligand. The bond distances found in the complex cation 152 (X = O) are compatible with a high-spin... 

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