1,10-Phenanthroline, nickel complex

C, H270PSi2, Phosphine, [23-dimethyl-l-(trimethylsiloxy)propylidene](tri-methylsilyl)-, 27 250 C 2HgN2, 1,10-Phenanthroline, nickel complex, 28 103... 

Nickel, tris(l, 10-phenanthroline) racemization, 1,24. 466 solid state, 1, 467 structure, 1,64 Nickel complexes, 5,1-300 acetylacetone alcoholysis, 2, 380 pyridine complexes, 2, 386 solvolysis, 2,379 structure, 2,388 amidines... 

Values are for the tris(l,10-phenanthroline)nickel(II) pentacarbonylmanganate complex. 

Later, a complete chromatographic resolution of Co(acac)3 and Cr(acac)3 on an optically active poly(triphenyhnethyl methacrylate) column was accomplished. The optical data of the pure enantiomers were obtained. Extensive use was made of columns composed of clay plus metal complex adducts. Thus, optical resolution was accomplished by LC on a column packed with an ion-exchange adduct of synthetic hectorite and optically active [Ni(II)](phen)3 and [Ru(II)](phen)3 . Using these systems, Co(acac)3, Cr(acac)3, Rh(acac)3 and [Co(acac)2(en)]+ (en = ethelenediamine) were resolved completely into enantiomers . Enantiomers of these four species were separated by LC on a column packed with ion-exchange adduct of synthetic hectorite and optically active metal complexes . One optically active metal complex used was tris(LlO-phenanthroline)-nickel(n), which was ion exchanged into synthetic hectorite. Racemic Co(acac)3, Cr(acac)3 and Ru(acac)3 were also enantiomerically separated via LC using poly(t-butylisocyanide) as stationary phase . ... 

Diastereoisomer formation with the optically active complex Z-tris(l,10-phenanthroline)nickel(II) cation has been shown by Dwyer and Sargeson to provide a rapid general resolution method for trioxalato complexes of Co(III), Cr(III), and Rh(III). The method, with modifications, is given below. 

The optical antipodes of tris(l,10-phenanthroline)nickel-(II) perchlorate are more stable than those of the corresponding tris(2,2 -bipyridine)[tris(2,2 -dipyridyl)] compound. In 18 hours, solutions of the 1,10-phenanthroline complexes lose only 50% of their activity. When examined at 589.0 and 546.1 m/x, the antipodes show a large abnormal rotatory dispersion. The precipitation of [Ni(o-phen)s]-[Co(CO)4]2 is the basis for a method of determining cobalt tetracarbonyl hydride. ... 

Because the Pfeiffer effect is exhibited by tris(l,10-phenanthroline)-nickel(II) ion and d-a-bromocamphor-7r-sulfonate and, because the complex has an absorption band in the visible region, this system was studied using optical rotatory dispersion techniques. The study revealed that the optical rotatory dispersion curves showing Pfeiffer rotation vs. wavelength were very similar to that of the resolved complex (Figures 3 and... 

Nucleophilic reactions of the spin-paired tris(o-phenanthroline) iron(II) ion are bimolecular 70-72). The tris complex is close to the spin-free complex in energy since dithiocyanatobis(o-phenanthroline) iron(II) exists in a spin-free = spin-paired equilibrium 53). The corresponding tris(o-phenanthroline)nickel(II) ion is unaffected by the same nucleophile, which probably rules out Sat2 attack on the organic ring as the predominant factor. 

The dyes Rhodamine 6G [55] and Crystal Violet [56] form extractable ion-associates with the anionic complexes of nickel with chloro-oxine [551 and 4-chloro-2-nitroso-l-naphthol [56], (e = 7.7-10 - 8.2-10 ). The ion associate of Rose Bengal with the cationic nickel complex with 1,10-phenanthroline, extractable into nitrobenzene, is also the basis of a sensitive method (e > 1-10 ) [57]. Hydroxynaphthol Blue has been applied for determination of Ni in the presence of Cu by the derivative spectrophotometry method [58]. 

COMPLEX TRI(ORTHO-PHENANTHROLINE)NICKEL(II) PATH LENGTH 1 DECIMETER SOLVENT WATER TEMPERATURE 23° C. CONCENTRATIONS COMPLEX - 0.02 MOLAR... 

Werner resolved the tris oxalate using strychninium ion in 1912. Other effective resolving agents for the tris complex include (+ )-tris(l,10-phenanthroline)nickel(II), ( + )- or (- )-tris(ethylenediamine)cobalt(III) and (- )-tris(ethylenediamine)rhodium(III). The (- )-[Co(ox)3] ion has been studied by single-crystal methods and has the d configuration. It has been related to (-i-)-[Cr(ox)3] by X-ray powder photography, so its absolute configuration is also established as d by the more exact form of the rule of least-soluble diastereoisomers. ... 

First, let us discuss the shapes of the chelated complexes. In most cases they are tetrahedral, but iron (both ferrous and ferric) forms octahedral complexes. However, the most remarkable contribution to selectivity is made by cupric ions which form planar complexes. This means that copper is uniquely sensitive to a type of steric effect imposed by bulky groups. Thus, in Table 11.2, the stability constants for the cupric complexes ofbipyridyl [11,19), phenanthroline [11.18), and folic acid lie below those of the corresponding nickel complexes, which is contrary to the natural order discussed in Section 11.2. 

The Chen group [26] has recently synthesized nickel complex 31 (Figure 5.7) with an NHC-tethered phenanthroline ligand. They have hypothesized that the NHC donor would increase the electron density at the nickel center while the phenanthroline unit could easily dissociate one of the N donors (presumably the outer one) to create a vacant coordination site, thereby facilitating the catalysis. This compound has proven to be a good catalyst (1 mol% loading) for the coupling of aryl chlorides... 

It has been established by X-ray analysis that in potassium (-b)58 -tris-(l,10-phenanthroline)nickel(ii) (—)5g,-trisoxalatocobaltate(m) dihydrate both complex ions have the A configuration. The mean Co-O distance is 1.93 A. The complex anion in sodium (- -)s4,-bismaIonatoethylenediamine-cobaltate(iii) has the A configuration the six-membered malonato chelate rings adopt boat conformations. ... 

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