We report a class of molecules with extremely low ionization enthalpies, one member of which has been determined to have a gas-phase ionization energy (onset, 3.51 electron volts) lower than that of the cesium atom (which has the lowest gas-phase ionization energy of the elements) or of any other known closed-shell molecule or neutral transient species reported. The molecules are dimetal complexes with the general formula M2(hpp)4 (where M is Cr, Mo, or W, and hpp is the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine), structurally characterized in the solid state, spectroscopically characterized in the gas phase, and modeled with theoretical computations. The low-energy ionization of each molecule corresponds to the removal of an electron from the delta bonding orbital of the quadruple metal-metal bond, and a strong interaction of this orbital with a filled orbital on the hpp ligands largely accounts for the low ionization energies.

To investigate the structural basis of triboluminescence, several known tetrahedrally coordinated Mn(II) complexes have been synthesized according to literature methods and their crystal structures have been determined by X-ray diffraction. Among them, (MePh(3)P)(2)[MnCl(4)] (2), a = 15.4804(4) A, cubic, space group P2(1)3, Z = 4; (Et(4)N)(2)[MnBr(4)] (4), a = 13.362(1) A, c = 14.411(1) A, tetragonal, space group P42(1)m, Z = 4; MnBr(2)(OPPh(3))(2) (7), a = 9.974(1) A, b = 10.191(3) A, c = 10.538(2) A, alpha = 65.32(1) degrees, beta = 63.49(1) degrees, gamma = 89.44(2) degrees, triclinic, space group P1, Z = 1; and MnBr(2)(OAsPh(3))(2) (10), a = 17.816(3) A, b = 10.164(1) A, c = 18.807(3) A, orthorhombic, space group Pca2(1), Z = 4 were reported to be triboluminescent and (Me(4)N)(2)[MnCl(4)] (3), a = 9.016(3) A, b = 36.90(2) A, c = 15.495(3) A, beta = 90.72(3) degrees, monoclinic, space group P2(1)/n, Z = 12, and MnI(2)(OAsPh(3))(2) (11), a = 10.094(4) A, b = 10.439(2) A, c = 34.852(2) A, alpha = 83.17(4) degrees, beta = 86.09(2) degrees, gamma = 75.16(3) degrees, triclinic, space group P1, Z = 4, were reported to be not triboluminescent. The result supports the correlation between space group acentricity and triboluminescence activity.

Chiral dirhodium(II) carboxamidates are highly efficient catalysts for reactions between a variety of aldehydes and activated dienes. Catalyst loadings as low at 0.01 mol % have been realized with enantioselectivities up to 97%. Kinetic investigations reveal a pronounced electronic influence on the rate of the hetero-DielsAlder reaction with a Hammett value of ؉1.9 (versus ؉ ). Inhibition of the catalyst by reactant aldehyde is apparent, but reactions show first-order dependence on aldehyde and diene, and there is a variable dependence on catalyst.

A series of compounds has been made containing quadruply bonded Re2(hpp)4X2 species (hpp = the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2a]pyrimidine), where X is CF3SO3 (1), CF3CO2 (2), and F (3). The distances of 2.1562(7), 2.1711(5), and 2.1959(4) A for 1-3 show significant effects of the sigma and pi electron donating ability of the axial ligands on the metal-metal distance. With the weakly coordinating triflate ligand the Re-Re distance is the shortest for any quadruple bonded species known. In addition to examining the effects of axial ligands on the Re2(hpp)42+ core, our study of the Re2(hpp)43+ core is being extended beyond the preliminary results previously reported in only one compound [Re2(hpp)4Cl2]PF6 (Dalton Trans. 2003, 1218). We now report the structural characterization by both X-ray and neutron diffraction of the compound [Re2(hpp)4F](TFPB)2, 4 (TFPB = the anion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate), and a detailed study by EPR spectroscopy of [Re2(hpp)4Cl2]PF6 at 9.5, 34.5, and 95 GHz frequencies, using dilute fluid solutions, frozen glass, and neat powder, show that the unpaired electron in the [Re2(hpp)4Cl2]+ ion is in an MO of predominant metal character with little mixing from the guanidinate ligands.