Of a-diimine complexes

Methyl acrylate ethene copolymerization The copolymer stmcture and the reaction mechanism of a-diimine complex-catalyzed copolymerization reactions with functionalized a-olefins are now described in detail for the ethene-MA copolymerization system.This will serve as a general example for a copolymerization of ethene with polar comonomers. In other specific cases, the nature of the rdevant steps may vary, but the general concept is applicable. 

In a series of studies of the spectroscopy and photochemistry of nickel(O) -a-diimine complexes, the structural differences among the complexes NiL2 and Ni(CO)2L (L Q-diimine) have been examined by means of molecular orbital calculations and electronic absorption Raman resonance studies.2471, 472 Summing up earlier work, the noninnocence of a-diimine ligands with a flat — N=C—C=N— skeleton in low-valent Ni chemistry and the course of substitution reactions of Ni° complexes with 1,4-diaza-1,3-dienes or a,a -bipyridine have been reviewed.2473... 

Bulk NLO studies on luminescent /uc- ReI(CO)3(a-diimine) + complexes by Yam and co-workers note SHG from surfactant derivatives such as (54) and (55) deposited in Langmuir-Blodgett (LB) thin films.110-112 For example, the 532 nm SHG from LB films of the stilbazole derivative (55) is ca. 50% more intense than that from films of the structurally related purely organic salt traiw-.lV-methyl-4-[2-(4-octadecyloxyphenyl)ethenyl]pyridinium iodide.112... 

The cubic NLO properties of Ru11 tris-(a-diimine) complexes have been investigated only relatively recently by Ji and co-workers using 540 nm Z-scan all of the complexes studied exhibit both NLO absorption and SDF behavior.135-138 The large and 7 values of complexes such as (73) depend on the position of the -N02 group in the order 4- > 2- > 3-.135 Also, the NLO responses decrease on deprotonation of the imidazolyl nitrogens (although this effect is only... 

Similar results were obtained for the redox reactions of a series of cobalt diimine complexes with cytochrome c (156, 157). In general a good agreement exists between the kinetically and thermodynami-... 

The first example of a helical complex with pre-determined chirality was the dinuclear complex [Fe2(rdt)3], where rdtFl2 is the fungal iron chelator rhodotorulic acid, (15), a dihydroxamate siderophore. Several more helical and chiral Fe " " and Fe complexes are documented in the diimine and in the hydroxamate and catechol sections. A doubly looped ( bow tie ) complex has been constructed with the aid of a tris-terimine ligand (Section 5.4.3.5.7). 

The mechanism depicted in Scheme 2 involves two main steps. Rupture of the first metal-nitrogen bond accompanied by coordination of a water ligand at the metal center is followed by reversible deprotonation and intramolecular reduction of the metal center. Under the experimental conditions wherein the concentration of base is much larger than the concentration of tris(diimine) complex, and, applying the steady-state approximation to the concentration of the intermediate species with the monodentate diimine ligand, Eq. (6) can be derived as... 

RR excitation profiles from a series of M(CO)4(a,a -diimine) complexes have identified additional y-polarized (dx2-z2) ai - b2 (n ) and x-polarized (dxy) a2 -> b2 (n ) MLCT transitions in the absorption band envelope, although the latter component is relatively weak for substituted phen derivatives [63], These absorption features are observable in the 80 K spectrum of W(CO)4(4-Me-phen) in EPA (see Fig. 2). The most intense MLCT components in the low-temperature spectrum appear at 444 and 468 nm, and these are associated with the ai -> b i and b2 -> b i transitions, respectively [60],... 

Low-valence transition metal complexes of a-diimine ligands are highly colored because of the presence of low-energy metal to a-diimine charge transfer (MLCT) transitions. For a series of d6-M(CO)., (a-diimine) (M=Cr,Mo,W) and d8- M (CO)3 (a-diimine) (M =Fe, Ru) complexes, we have studied the spectroscopic and photochemical properties (1-10). The a-diimine ligands used are 1,4-diaza-1,3-butadiene (R-DAB), pyridine-2-car-baldehyde-imine (PyCa), 2,2 -bipyridine (bipy) or 1,10-phenanthroline (phen) molecules. A close relationship was deduced between the photochemical behavior of these complexes and their resonance Raman (rR) spectra, obtained by excitation into the low-energy MLCT band. 

Protonation and Reductive Elimination Reaction of a (Diimine)platinum (II) Dimethyl Complex It has been realized for some time that direct, selective methods for catalytic conversion of hydrocarbons to products of further value are important goals for chemistry investigators. This topic is notably complex and may be reviewed for the considerable body of research conducted heretofore.348-350 Aqueous... 

Although ferryl intermediates of horseradish peroxidase and microperoxidase-8 have been produced in reactions with photogenerated [Ru(bpy)3]3+ [5], analogous experiments with P450s were unsuccessful, presumably due to the inefficiency of electron transfer from the buried heme active site through the protein backbone [6]. Photoactive molecular wires (sometimes referred to as metal-diimine wires, sensitizer-tethered substrates, or electron tunneling wires) were developed to circumvent this problem by providing a direct ET pathway between [Ru(bpy)3]3+ and the heme. These molecular wires, which combine the excellent photophysical properties of metal-diimine complexes... 

Turro C, Hall DB, Chen W, Zuilhof H, Barton JK, Turro NJ. Solution photoreactivity of phenanthrenequinone diimine complexes of rhodium and correlations with DNA photocleavage and photooxidation. / Phys Chem A 1998 102 5708-15. 

---