Claisen condensation of acetyl ruthenocene with the appropriate methyl ester, RCOOMe, under the influence of the hindered base lithium diisopropylamide gave the -diketones (RcCOCH 2 COR) 1-ruthenocenyl-4,4,4-trifluorobutane-1,3-dione (ruthenocenoyltrifluoroacetone, 1, R ) CF 3 ; pK a ′ ) 7.36 ( 0.03), 1-ruthenocenylbutane-1,3-dione (ruthenocenoylacetone, 2, R ) CH 3 ; pK a ′ ) 10.22 ( 0.01), 1-phenyl-3-ruthenocenylpropane-1,3-dione (benzoylruthenocenoylmethane, 3, R ) C 6 H 5 ; pK a ′ ) 11.31 ( 0.03), 1-ferrocenyl-3-ruthenocenylpropane-1,3-dione (ferrocenoylruthenocenoylmethane, 4, R ) Fc ) (C 5 H 5 )Fe(C 5 H 4 ) ) ferrocenyl; pK a ′ ) ca. 12.8), and 1,3-diruthenocenylpropane-1,3-dione (diruthenocenoylmethane, 5, R ) Rc ) (C 5 H 5 )Ru(C 5 H 4 ) ) ruthenocenyl; pK a ′ ) ca. 12.7). The group electronegativity of the ruthenocenyl group, Rc ) 1.89 on the Gordy scale, was obtained from the linear relationship between IR carbonyl stretching frequencies of a series of methyl esters, RCOOMe, and R . A 1 H NMR kinetic study of the enol-keto interconversion resulted in accurate equilibrium constants, K c , for this equilibrium, as well as forward and reverse rate constants of the isomerization process. Cyclic voltammetry in CH 3 CN/N( n Bu) 4 PF 6 utilizing a glassy-carbon electrode showed the ruthenocene center exhibited, in contrast to the ferrocene center, irreversible electrochemistry. The multiple peak anodic (oxidation) potentials observed are a consequence of slow isomerization kinetics and made peak assignments for the keto and enol isomers possible. The kinetics of enol to keto isomerization for 4 was also studied by cyclic and Osteryoung square wave voltammetry; obtained rate constants were mutually consistent with those obtained by the 1 H NMR technique. Kinetic rate constants, K c , and pK a ′ and E p,a were related to R values of the R groups in RcCOCH 2 COR.

The solution phase behaviour of non-peripherally substituted octa-hexyl cadmium phthalocyanine 3 and peripherally substituted octa-2-ethylhexyl cadmium phthalocyanine has been investigated in fresh solutions of CH(2)Cl(2), CHCl(3)-d(1) and THF/THF-d(8) using (1)H NMR spectrometry, UV-Vis spectroscopy, cyclic voltammetry, square wave voltammetry and linear sweep voltammetry. The compounds show an unexpected propensity to form dimeric species in CH(2)Cl(2) and CHCl(3)-d(1), and, in the case of , also to a lesser extent in THF/THF-d(8). This phenomenon is not observed for their metal-free analogues or . The electrochemical results provide particularly strong evidence for the dimeric structures. In particular both the first one-electron oxidation and one-electron reduction waves for 3 and 4, unlike those of and , are split. This is consistent with sequential oxidation/reduction of the two Pc ligands within a dimer. The dimeric species are likely to be the immediate precursors of the recently discovered bis-cadmium tris-phthalocyanine triple-decker sandwich complexes and formed from and over a period of time. The electrochemical data for compounds also show that (i) relative to the metal-free phthalocyanines, the cadmium phthalocyanines exhibit smaller formal reduction potentials for all but one of the observed electron transfer processes and (ii) the electron transfer processes associated with the peripherally substituted compounds, 2 and 4, are observed at more positive potentials than those for the corresponding non-peripherally substituted analogues 1 and 3.

The electronic and electron transfer behaviour of two examples of a recently discovered class of triple-decker sandwich complex based on three phthalocyanine ligands linked by two chelated cadmium ions has been investigated by EPR spectroscopy and cyclic voltammetry, square wave voltammetry and linear sweep voltammetry experiments. The two compounds, and , differ in the location of the eight alkyl groups attached to each of the phthalocyanine rings; at the non-peripheral sites in and the peripheral sites in . Quantitative comparison of the free radical character of and in solutions was undertaken by EPR spectroscopy and revealed that exists as a mixture of s = 0 and s = (1/2) species, whereas compound exists essentially as a spin (1/2) species alone. The electrochemical study of and was undertaken in both dichloromethane (CH(2)Cl(2)) and tetrahydrofuran (THF). The two compounds show comparable but subtly different redox behaviour which can only be attributed to the different locations of the substituents. Seventeen of the possible eighteen one-electron transfer processes could be identified for . The first oxidation wave for , both in THF and in CH(2)Cl(2) solutions, was encountered at ca. 160 mV lower potential than for implying that is much easier to initially oxidise than . This finding provides a rationale for the EPR results described above. In separate experiments, oxidation of and as solutions and spin-coated film formulations was achieved using iodine and was characterised by significant changes in the visible region absorption spectra of the compounds.

Non-peripherally octakis-substituted phthalocyanines (npPc’s), MPc(C12H25)8 with M = 2H (3) or Zn (4), as well as peripherally octakis-substituted phthalocyanines (pPc’s) with M = Zn (6), Mg (7) and 2H (8), were synthesized by cyclotetramerization of 3,6- (2) or 4,5-bis(dodecyl)phthalonitrile (5), template cyclotetramerization of precursor phthalonitriles in the presence of Zn or Mg, metal insertion into metal-free phthalocyanines, and removal of Mg or Zn from the phthalocyaninato coordination cavity. The more effective synthetic route towards pPc 8 was demetalation of 7. npPc’s were more soluble than pPc’s. The Q-band λmax of npPc’s was red-shifted with ca. 18 nm, compared to that of pPc’s. X-ray photoelectron spectroscopy (XPS) differentiated between N–H, Nmeso and Ncore nitrogen atoms for metal-free phthalocyanines. Binding energies were ca. 399.6, 398.2 and 397.7 eV respectively. X-ray photoelectron spectroscopy (XPS) also showed zinc phthalocyanines 4 and 6 have four equivalent Nmeso and four equivalent N–Zn core nitrogens. In contrast, the Mg phthalocyanine 7 has two sets of core N atoms. One set involves two Ncore atoms strongly coordinated to Mg, while the other encompasses the two remaining Ncore atoms that are weakly associated with Mg. pPc’s 6, 7, and 8 have cyclic voltammetry features consistent with dimerization to form [Pc][Pc+] intermediates upon oxidation but npPc’s 3 and 4 do not. Metalation of metal-free pPc’s and npPc’s shifted all redox potentials to lower values.

The synthesis of the first rhodium(I) cyclooctadiene complexes containing tetrathiafulvalene (TTF) groups substituted on a beta-diketonato ligand in either the methine position (3 position), [Rh(cod)(H(3)CCOC{S-TTF-(MeS)(3)}COCH(3))] (3), or terminal position (1 position), [Rh(cod){(Me(3)-TTF)COCHCOCH(3)}] (4), is reported. The effect of the beta-diketonato substitution position on the kinetics of substitution of the TTF-containing beta-diketonato ligand with 1,10-phenanthroline from 3 and 4 to give [Rh(cod)(phen)](+), as well as on the electrochemical properties of 3 and 4, was investigated. Second-order substitution rate constants, k(2), in methanol were found to be almost independent of the substitution position, with 4 (k(2) = 2.09 x 10(3) dm(3) mol(-1) s(-1)) reacting only about twice as fast as 3. An appreciable solvent pathway in the substitution mechanism was only observed for 4 with k(s) = 42 s(-1). A complete mechanism for both substitution reactions is proposed. The electrochemistry of 3 and 4 in CH(2)Cl(2)/0.10 mol dm(-3) [N((n)Bu)(4)][B(C(6)F(5))(4)] showed three redox processes. Two of these were electrochemically reversible and are associated with the redox-active TTF group. For 3, TTF-based formal reduction potentials, E degrees', were observed at 0.082 and 0.659 V vs Fc/Fc(+), respectively; 4 exhibited them at -0.172 and 0.703 V vs Fc/Fc(+) at a scan rate of 100 mV s(-1). A Rh(II)/Rh(I) redox couple was observed at E degrees' = 0.89 V for 3, after both TTF oxidations were completed, and at 0.51 V for 4; this is between the two TTF redox processes. The more difficult oxidation of the Rh(I) center of 3 indicates more effective electron-withdrawing from the Rh(I) center to the first-oxidized TTF(+) group at the methine position of the beta-diketonato ligand of 3(+) than to the terminal-substituted TTF(+) group in 4(+).