NO as ligand

Very recently, the kinetics and thermodynamics of a variety of axial ligation reactions have been investigated with Fe11 and Co11 porphyrins involving the small molecules CO, 02, and NO as ligands 27-30, 40, 92, 93). These experiments lead to the conclusion that the dynamic trans effects observed in these systems cannot alone be explained by the interaction models D and F (Fig. 1). Especially imidazole and its derivatives do not hold the place in various series of trans effects that they should take on the ground of their proton basicities. Therefore, besides their usual a-donor-tr-acceptor function, these unsaturated molecules are ascribed an additional 7r-donor function. 

A comparison of several different steroid receptors with thyroid hormone receptors revealed a remarkable conservation of the amino acid sequence in certain regions, particularly in the DNA-binding domains. This led to the realization that receptors of the steroid or thyroid type are members of a large superfamily of nuclear receptors. Many related members of this family have no known ligand at present and thus are called orphan receptors. The nuclear receptor superfamily plays a critical role in the regulation of gene transcription by hormones, as described in Chapter 43. 

Another group of orphan receptors that as yet have no known ligand bind as homodimers or monomers to direct repeat sequences. 

These teceptors, which may have hormones, metabolites, ot dmgs as ligands, bind to specific DNA elements as homodimers or as heterodimers with RXR. Some—orphan receptors—have no known ligand but bind DNA and influence transcription. 

Recent years, the authors have innovatively proposed a method by using the aqueous ammonia liquor containing hexamine cobalt (II) complex to scrub the NO-containing flue gases[6-9], since several merits of this complex have been exploited such as (1) activation of atmospheric O2 to a peroxide to accelerate the O2 solubility, (2) coordination of NO, as NO is a stronger ligand than NH3 and H2O of Co( II) complexes to enhance the NO absorption and (3), catalysis of NO oxidation to further improve the absorption both of O2 and NO. Thus, a valuable product of ammonium nitrate can be obtained. 

As heavier analogs of carbenes141) stannylenes can be used as ligands in transition-metal chemistry. The stability of carbene complexes is often explained by a synergetic c,7t-effect cr-donation from the lone electron pair of the carbon atom to the metal is compensated by a a-backdonation from filled orbitals of the metal to the empty p-orbital of the carbon atom. This concept cannot be transferred to stannylene complexes. Stannylenes are poor p-a-acceptors no base-stabilized stannylene (SnX2 B, B = electron donor) has ever been found to lose its base when coordinated with a transition metal (M - SnXj B). Up to now, stannylene complexes of transition metals were only synthesized starting from stable monomoleeular stannylenes. Divalent tin compounds are nevertheless efficient cr-donors as may be deduced from the displacement reactions (17)-(20) which open convenient routes to stannylene complexes. 

In comparison to the two other described educt compounds 4a and 18, the anions of 31a and 31b can also be prepared in a one step synthesis in satisfying yields, without the application of high pressure conditions starting from 3a or 19a. This compound should open intensive exploration of Tc(I) and Re(I) chemistry. In contrast to the other two educts, no competing ligands are present. The halides bind only very weakly and the carbonyls are easily withdrawn from equilibrium by volatility. As shown in the previous section, a number of examples illustrate the versatility of this educt. It can be applied not only for substitutions in organic solvents but also in water, and therefore allows reactions with ligands that are... 

Compounds (L)AuC=CR can appear as ligands in the coordination sphere of transition metals. The interaction may be fluxional with metal-metal contacts M-Au and the alkyne coordinated side-on (if, dihapto) to the gold atom. Typical examples are (cp)(CO)(NO)W[Ph3PAuC=C Bu 90 and l, c3(CO)9[R3PAuC=CtBu], with R = Ph, Pr, for which several isomers have been observed in solution.91... 

---