Obesity may be protective compared with thinness or normal weight in older community-dwelling Americans.

A chronological survey of the syntheses and characterizations of homoleptic mononuclear metal carbonyl anions is presented, from the first isolated example, [Fe(CO)4]2-, to the most recently reported species, [Hf(CO)6]2-. These materials are of historical interest, since they are the first compounds to contain transition metals in formal negative oxidation states, but remain important reagents in all areas of chemical synthesis and often closely resemble electron-rich nonmetallic compounds in their ability to function as Lewis and Brønsted bases, nucleophiles, and/or reducing agents. Prospects for the syntheses of new carbonyl anions for the very early and late transition metals and the lanthanides and actinides are also discussed.

A brief history of substances containing s,p- and d-block metals in negative oxidation states is described. A classification of these species and discussions of formal oxidation state assignments for low-valent transition metals in complexes are included, along with comments on the innocent and noninnocent character of ligands in metalates. Syntheses of highly reduced carbonyl complexes formally containing transition metals in their lowest known oxidation states of III- and IV- are discussed. Atmospheric-pressure syntheses of early-transition-metal carbonyls involving alkali-metal polyarene-mediated reductions of non-carbonyl precursors have been developed. In the absence of carbon monoxide, these reactions afford homoleptic polyarenemetalates, including the initial species containing three aromatic hydrocarbons bound to one metal. In several instances, these metalates function as useful synthons for "naked" spin-paired atomic anions of transition metals.

Gallamine allosterically modulates the binding of classical muscarinic ligands with a potency order of M(2) > M(1),M(4) > M(3), M(5). We have suggested previously that the M(2)/M(5) and M(2)/M(3) selectivities are attributable to an epitope in the sixth transmembrane region or third outer loop (o3) region of the receptor. In this study, analysis of numerous point mutations in this region of the M(5) receptor found that a mutation of V --> N resulted in an increased affinity toward gallamine, suggesting that the asparagine residue at M(2)(419) is responsible for gallamine's M(2)/M(5) selectivity. Mutations in the other subtypes indicated that the acidic residues found at this position in M(1) and M(4) are associated with slightly higher affinity toward gallamine, whereas the valine and lysine residues of M(5) and M(3), respectively, are associated with significantly lower affinity. In the o2 region, replacement of an acidic sequence of M(2) (EDGE) by the corresponding neutral sequence of M(1) (LAGQ) reduced the affinity toward gallamine, as reported previously by others; the converse substitution of the acidic sequence into M(1) significantly increased affinity for gallamine. Substitution of the M(1) sequence into this region of M(5) markedly reduced affinity toward gallamine, whereas substitution into M(4) had no effect. All of the above mutations are consistent with gallamine binding with a similar orientation at each subtype, such that it interacts with acidic residues in the o2 region of M(3) and M(5) and with acidic residues in the o3 region of M(1) and M(4); gallamine appears to interact with both regions of the M(2) subtype.