Correlation of the Rates of Solvolysis of the Benzhydryldimethylsulfonium Ion. Application of the Aromatic Ring Parameter(1)

Values for the specific rates of solvolysis of the benzhydryldimethylsulfonium ion in 34 solvents have been analyzed using various forms of the extended Grunwald-Winstein equation. The specific rates are insensitive toward changes in solvent nucleophilicity (N(T)) values, and they correlate best against a combination of Y(+) values (based on the solvolyses of the 1-adamantyldimethylsulfonium ion) and aromatic ring parameter (I) values. Common-molecule return is observed, being especially powerful in solvents rich in fluoro alcohol; the logarithm of the associated mass law constant correlates inversely with the solvent N(T) values. The product selectivities in ethanol-water mixtures are also consistent with an S(N)1 mechanism for the solvolyses.     

Solid-state changes in ligand-to-metal charge-transfer spectra of (NH3)5Ru(III)(2,4-dihydroxybenzoate) and (NH3)5Ru(III)(xanthine) chromophores

Five distorted-octahedral complexes containing (NH3)5Ru(III)L ions, where L = 2,4-dihydroxybenzoate or a xanthine, have been studied using a combination of X-ray crystallography, solution and polarized single-crystal electronic absorption spectroscopy, and first principles electronic structure computational techniques. Both yellow (2) and red (3) forms of the complex (NH3)5Ru(III)L, where L = 2,4-dihydroxybenzoate, as well as three xanthine complexes in which L = hypoxanthine-kappaN(7) (4), 7-methylhypoxanthine-kappaN(9) (5), and 1,3,9-trimethylxanthine-kappaN(7) (6) were examined. In the solid state, some of these complexes exhibit split low-energy ligand-to-metal charge-transfer (LMCT) bands. Traditional solid-state effects, such as ligand pi-pi overlap or hydrogen bonding that might lead to splitting of electronic absorption bands, were probed in an attempt to identify the origins of these unusual observations. For comparison, companion studies were carried out for spectroscopically normal reference complexes of the same ligands. Time-dependent density-functional theory (TD-DFT) calculations, employing modified B3LYP-type functionals with increased contributions of exact exchange, attribute the color change in the crystalline complexes 2 and 3 to pi(ligand) --> Ru[d(pi)] LMCT bands which, in the red form (3), arise from ligand donor pi-orbitals split by strongly overlapping phenyl moieties in centrosymmetric (NH3)5Ru(III)(2,4-dihydroxybenzoate) dimers. Complex 5 does not show split visible absorptions, whereas both the polarizations and energies of the split visible absorptions shown by 4 and 6 also suggest assignment as LMCT. No support is found for relating the split absorptions of 4 and 6 to the details of pi-pi xanthine overlap in the solid state; indeed, complex 4 enjoys considerably less pi-stacking overlap than does 5. We feel compelled to attribute the split absorptions in crystalline 4 and 6 to the emergence of a LMCT transition originating in the carbonyl lone pair, potentially deriving intensity from the significant intramolecular N-H...O hydrogen bonding present in both 4 and 6 (but not in 5). The electronic structure calculations suggest an O(n) --> Ru[d(sigma*)] LMCT transition; however, this novel assignment must be considered tentative.     

ChemInform Abstract: 3s-Gd2C2Br2, an Isomorph with a New Stacking Sequence

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