Amines 175 phenanthrolines

Phosphorus pentahalides can react with a great variety of organic bases to form adducts, at least some of which are probably inner onium-ate compounds containing 6-coordinated P atoms. These bases include pyridine, tertiary amines, phenanthroline, symm dimethylurea, tertiary phosphine oxides and so forth (6.551, 6.552). Another onium-ate or zwitterionic phosphoride (6.553) can be made from the diphosphorane (6.540). 

Crystal stmctures of complexes of copper(II) with aromatic amine ligands and -amino acids " " and dipeptides" have been published. The stmctures of mixed ligand-copper complexes of L-tryptophan in combination with 1,10-phenanthroline and 2,2 -bipyridine and L-tyrosine in combination with 2,2 -bipyridine are shown in Figure 3.2. Note the subtle difference between the orientation of the indole ring in the two 1,10-phenanthroline complexes. The distance between the two... 

Like mthenium, amines coordinated to osmium in higher oxidation states such as Os(IV) ate readily deprotonated, as in [Os(en) (NHCH2CH2NH2)] [111614-75-6], This complex is subject to oxidative dehydrogenation to form an imine complex (105). An unusual Os(IV) hydride, [OsH2(en)2] [57345-94-5] has been isolated and characterized. The complexes of aromatic heterocycHc amines such as pyridine, bipytidine, phenanthroline, and terpyridine ate similar to those of mthenium. Examples include [Os(bipy )3 [23648-06-8], [Os(bipy)2acac] [47691-08-7],... 

Amorphous (most likely atactic) 3,4-polyisoprene of 94—100% 3,4-microstmcture was prepared with a (C2H 3A1—Ti(0—/ -C Hy) catalyst (11). Crystalline 3,4-polyisoprene containing about 70% 3,4-units and about 30% i7j -l,4-microstmcture was prepared using a catalyst derived from iron acetyl acetonate, trialkyl aluminum, and an amine in benzene (37). However, this polyisoprene contained gel and was obtained in poor yield. Essentially gel-free crystallizable 3,4-polyisoprene of 70—85% 3,4-microstmcture with the remainder being cis-1,4 microstmcture was prepared in conversions of greater than 95% with a water-modified tri alkyl aluminum, ferric acetyl acetonate, and 1,10-phenanthroline catalyst (38). The 3,4-polyisoprene is stereoregular and beheved to be syndiotactic or isotactic. 

Reduction in compression set began to be achieved in the late 1960s when it was found that tropolene and phenanthroline not only accelerated amine cures but were also effective with certain bisnucleophiles such as resorcinol, hydroquinone and bis-phenol AF. In due course even better results were obtained with quaternary ammonium or phosphonium salts being used in conjunction with aromatic dihydroxy compounds. 

These oxidants are generally too feeble to attack monofunctional compounds except thiols, carbonyl- and nitro-compounds in their enolic forms, phenols and aromatic amines. However, ferric rWj-o-phenanthroline readily oxidises cyclohexanone. 

Some other examples of metal-catalyzed substitutions are given in Scheme 11.10. Entries 1 to 3 are copper-catalyzed reactions. Entry 1 is an example of arylation of imidazole. Both dibenzylideneacetone and 1,10-phenanthroline were included as ligands and Cs2C03 was used as the base. Entry 2 is an example of amination by a primary amine. The ligand used in this case was (V,(V-diethyl sal icyl amide. These conditions proved effective for a variety of primary amines and aryl bromides with both ERG and EWG substituents. Entry 3 is an example of more classical conditions. The target structure is a phosphodiesterase inhibitor of a type used in treatment of asthma. Copper powder was used as the catalyst. 

Condensation of l,0-phenanthroline-2-carbaldehyde with a series of primary amines produces terimine systems in which the field can be varied in relatively small steps, leading to a continuous spin transition in the [Fe N6]2+ complex of the system obtained from the bulky t-butylimine 68 [107]. Similarly hydrazones may be obtained, the most important of which, in the present context, is the phenyl-hydrazone 69 (phy) [108]. 

Tri (rt-butyl)phosphate (TBP), 79 674 Tri-l,10-phenanthroline-iron(II), 7 589 1-Triacontanol physical properties of, 2 3t cis-21-Triacontenoic acid physical properties, 5 32t Triacetate chiral stationary phase, 6 88t Triacetate fibers, 24 614 Triacetone amine... 

A number of thermodynamic studies of Ni[R-dtp)2 adducts with amines have been described H2,i43,is6,is8) Daktemieks and Graddon ) have measiued the enthalpies of addition of pyridine, 4-picoline, 2,2 -dipyridyl and 2,9-dime-thyl-l,10-phenanthroline to Ni[ethyl-dtp]2 and pyridine to Nilpropyl-dtpJj. The sums of the stepwise enthalpies for pyridine addition to the ethyl and... 

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