The reactions of ammonia, pyridine (py), N-methyl imidazole (N-MeIm), tetrahydrothiophene (tht), and piperidine (pip) with Re(CO) 3(H 2O) 3 (+), 1 ( + ), were investigated employing aqueous conditions under atmospheric dioxygen. The reaction of [ 1]Br in aqueous ammonia led to [Re(CO) 3(NH 3) 3]Br ([ 2]Br) as the only product isolated. For the aqueous reactions of [ 1]Br with py, N-MeIm, and tht, mixtures of products are formed because of competition between the bromide and added ligand, even when the ligand is present in excess. Substitution of the PF 6 (-) anion for Br (-) leads to the clean formation of [Re(CO) 3L 3][PF 6] ([ 3][PF 6]-[ 5][PF 6]) for py, N-MeIm, and tht, respectively, as the only products observed. Reaction of [ 1][PF 6] with pip produces the dimeric species, (pip)(CO) 3Re(micro-OH) 2Re(CO) 3(pip), 6. Reactions of [ 1]Br were also performed in methanol for comparison purposes. The reaction with pip in this solvent led to the analogous dimer, (pip)(CO) 3Re(micro-OMe) 2Re(CO) 3(pip), 7; however, reactions with py, N-MeIm, and tht gave Re(CO) 3L 2Br, 8- 10, respectively, as the only products. The crystal structures of compounds [ 2]Br- 10 are reported.

The first nickel complexes of two carbon-substituted phthalocyanine analogues are reported; both exhibit direct Ni-C bonding and oxygen activation chemistry is observed.

The reaction of Re(CO)(5)Br with tris(2-pyridyl)methanol (tpmOH) leads to unexpectedly complex chemistry with three new compounds forming instead of a single product. In compound 1, the tpmOH ligand binds to the metal in the N,N',N''-mode; 2 has tpmO(-) bound in the N,N',O-mode; while 3 is a dimer with the tpmO(-) ligand utilizing each of the four donor atoms to bridge the two metal centers. The analogous methyl ether ligands, tris(2-pyridyl)methoxymethane (tpmOMe) or tris[2-(l-methylimidazolyl)]methoxymethane (timmOMe), each yielded a single product, 4 and 5, respectively, bound in the N,N',N''-mode, and are new leads for potential radiotherapeutic agents. All compounds have been structurally characterized.

In this report we present an X-ray crystallographic study of two N -deficient hemiporphyrazines: dicarbahemiporphyrazine (1) and benziphthalocyanine (2). Both compounds can be isolated in multiple crystal forms, and five different solvated forms of macrocycle 1 are presented. Four of the five are non-planar, showing the high degree of flexibility and capacity for hydrogen bonding from solvent to N-H groups in the macrocycle. The remaining structure of 1 is a planar dicationic species that represents a tautomeric form of the macrocycle often seen in metal binding. Four structures of macrocycle 2 are also presented in this report. The structure of 2 is also planar due to the tautomerism of the internal protons, and structural elucidation of this macrocycle reveals the presence of three ionizable protons rather than the expected single proton postulated by Elvidge and Golden.