Metal ion adducts

Alkyl derivatives such as 1,4-S6(NR)2 and S4(NR)4 can be synthesized by reacting S2CI2 with primary amines RNH2 in an inert solvent. Compounds such as 1,4-S2(NR)4 (R = —C02Et) are now also well characterized.The bis-adduct [Ag(S4N4H4)2]" " has been isolated as its perchlorate this has a sandwich-like structure and is unique in being S-bonded rather than N-bonded to the metal ion. ... 

The catalytic activity of the N4 complexes depends both on the nature of the central metal ion and on the nature of the ligand and aU substituents. It was found that the metal ion is the active site where the electrocatalytic process is accomplished. During its adsorption, an oxygen molecule forms a stable complex (adduct) with the... 

A large number of type 1 dioxygen adducts are reported in the literature (25, 76, 80). The vast majority of metal complexes which take up dioxygen to form type I adducts contain cobalt(ll) as the metal ion. Ochiai (81) considered the hypothetical reactions ... 

Radical attack yields nucleobase radical adducts that must undergo either oxidation or rednction to yield a stable final prodnct. The cellular oxidant in these reactions may be molecnlar oxygen or high-valent transition metal ions (e.g., Fe ), while the reduc-tant may be either thiols, snperoxide radical, or low-valent transition metal ions (e.g., Fe ). In many cases, the base remains largely intact and the seqnence of chemical events can be readily inferred. In some other cases, more extensive base decomposition occurs. Here, we will consider a set of representative examples that provide a framework for understanding virtnally all radical-mediated base damage reactions. 

A detailed description of sources used in atmospheric pressure ionization by electrospray or chemical ionization has been compiled.2 Atmospheric pressure has been used in a wide array of applications with electron impact, chemical ionization, pressure spray ionization (ionization when the electrode is below the threshold for corona discharge), electrospray ionization, and sonic spray ionization.3 Interferences potentially include overlap of ions of about the same mass-charge ratio, mobile-phase components, formation of adducts such as alkali metal ions, and suppression of ionization by substances more easily ionized than the analyte.4 A number of applications of mass spectroscopy are given in subsequent chapters. However, this section will serve as a brief synopsis, focusing on key techniques. 

The presence of /3-hydrogen in the nitroxide radical may lead to disproportionation reactions. In spin-trapping experiments, N-t-butyl-a-phenyl nitrone yields rather unstable spin adducts. This type of radical can be stabilized by coordination to Nin. The Ni11 complex with N-oxy-A-r-butyl-(2-pyridyl)phenylmethanamine (923) reveals a distorted octahedral geometry with antiferromagnetic interactions between the unpaired electrons of the metal ion and the radical spins.00... 

The metal ion, e.g. Fe or Co, when in its lower oxidation state can share electron charge with the oxygen molecule adduct. Several iron and cobalt prophyrin derivatives and cobalt-Schiff bases show the necessary reversibility and rates for successful application [e.g. 23]. a, a, a", a" -weso-tetrakis[(o-piralamidophenyl)-po phinato] Co (II) has been complexed with 1-methylimidazole to make a complex (CoPIm) which, when mixed with polybutyl methacrylate gave oxygen permeabilities on the order of 10-9 sec-cm/(cm2-s-cmHg) with a selectivity of about 5 over nitrogen [23]. 

In our laboratory we have utilized multiphoton infrared laser activation of metal ion-hydrocarbon adducts to probe the lowest energy pathways of complex reaction systems (6). Freiser and co-workers have utilized dispersed visible and uv radiation from conventional light sources to examine photochemical processes involving organometallic fragments... 

The stability of metal ion-alkane adducts such as shown in Figure 11 remains an interesting question. The bonding in such systems can be regarded as intermolecular "agostic" interactions (46). Similar adducts between metal atoms and alkanes have been identified in low-temperature matrices (47). In addition, weakly associated complexes of methane and ethane with Pd and Pt atoms are calculated to be bound by approximately 4 kcal/mol (43). The interaction of an alkane with an ionic metal center may be characterized by a deeper well than in the case of a neutral species, in part due to the ion-polarization interaction. 

For consistency, an initial well associated with the formation of an adduct of the metal ion with the alkane should be included in Figure 11. The chemical activation associated with the formation of such an adduct is likely to be essential in overcoming intrinsic barriers associated with insertion into C-H bonds. In comparison to larger hydrocarbons, the weaker interaction of ethane with first row group 8-10 metal ions may be insufficient to overcome intrinsic barriers for insertion. This would explain the failure to observe dehydrogenation of ethane by these metal ions, even though the process is known to be exothermic. The well depths could be determined from high pressure equilibria. Studies in our laboratory and elsewhere have indicated the ease with which many of... 

To reduce the high level of internal excitation which results from association of the metal ion with the olefin, adducts are prepared using the ligand exchange reaction 14 and the product is allowed to further... 

The hemispherands, spherands, calixarenes, and related derivatives. A number of hosts for which the pre-organization criterion is half met (the hemispherands) (Cram et al., 1982) or fully met (the spherands) (Cram, Kaneda, Helgeson Lein, 1979) have been synthesized. An example of each of these is given by (251) and (252), respectively. In (251), the three methoxyl groups are conformationally constrained whereas the remaining ether donors are not fixed but can either point in or out of the ring. This system binds well to alkali metal ions such as sodium and potassium as well as to alkylammonium ions. The crystal structure of the 1 1 adduct with the f-butyl ammonium cation indicates that two linear +N-H - 0... 

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