THE STUDY OF THE REACTION OF THE QUASI-AROMATIC COMPLEX [Ni(PnAO)-6H]^(?)WITH FORMALDEHYDE: KINETICS AND MECHANISM

The kinetics of the reaction of [Ni(PnAO)—6H]° with formaldehyde was studied in H_2O—CH_3OH solution under neutral condition and a complicated mechanism with three steps including competitive, consecutive and reverse reactions was proposed.

Studies on Electrophilic Substitution of Quasi-Aromatic Metal Ion Complexes

The electrophilic substitution reaction occurring to the chelate ring of the complexes could be regarded as an indication of quasi-aromaticity of the ring systems, no catalyst was used and only triethylamine was employed, implying that the aroylating agents with different p-substituents are polarized enough to be effective electrophiles to attack the methine carbon of the electron-rich substrate 1. This property is probably the clue to polarization of the ligand electrons by the nickel( Ⅱ ) ion and to the participation of the nickel( Ⅱ ) in the π-bond systems of the two coordinated conjugated rings. The linearity relationship between vd-d maxima, E1/2OX(1) and σp are obtained, respectively. The electronic environment of central metal ion as well as the aromaticity of the ring system are affected by the electronic properties of the p-substituents. A comparison of the electrochemical results with each other showed .that when the electronegativity of the substituent was higher, the oxidation(Ni2+/Ni3+) becomes more difficult.

Quasi-aromaticity in Cluster Chemistry Ⅲ. Localized Molecular Orbital Study on Electron-rich Cobalt-sulfur Cluster Compounds[Co_6(μ_3-X)_8L_6]￣(n+)(X=S,Se;L=PPh_3,PEt_3,CO;n=0,1)

The localized molecular orbitals and energy levels for [Co_6 (μ_3-S)_8 (PH_3)_6]￣(n+)(n=0, 1) as model molecules of the electron-rich [Co_6 (μ_3-S)_8 (PPh_3)_6]￣(n+) (n=0,1) cluster compounds have been calculated by using Edmiston-Ruedenberg energy localization scheme under the spin-unrestricted CNDO/2 approximation. It is shown that the cluster skeletons of these two isostructural molecules consist of the edge-localized two-centered two-electron (Co-S) bonds plus a pair of the skeleton electrons delocalized on the whole cluster core,leading an extra stability of the cluster core.The one-electron oxidation for the neutral molecule gives rise to a one-electron σ (Co-Co) bond.which further resonates among the three diagonal lines of the {Co_6} octahedron. The comparison between [Co_6 (μ_3-S)_8(PPh_3)_6] and [Co_6(μ_3-CO)_8(CO)_6]￣(4-) indicates that the latter possesses face-localized bridging-bonds which are further delocalized on the whole surface of the cluster octahedron by the back-donation bonds from the lone electron pairs on the Co atoms to the capping carbonyl CO ligands. The structural features of the series of the [Co6(μ_3-X)_8L_6]￣(n+)(X =S, Se; L=PPh_3,PEt_3, CO;n=0, 1) cluster compounds are briefly rationalized on the basis of the localization description as well.

Quasi-aromaticity in Cluster Chemistry Ⅱ. Localized Molecular Orbital Studies on Co_6 (CO)_(14)^(4-) and Ni_2Co_4 (CO)_(14)^(2-) Cluster Anions

The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)]￣(4-) and [Ni_2Co_4 (CO)_(14)]￣(2-)in order to get a deeper insight into the nature of their skeletal bonding. The bonding characteristics of these hexanuclear carbonyl cobaltates are described from a localization bonding viewpoint. There are two typical M-CO bondings, one of which is formed by electron donation from the terminal and capping carbonyl ligands into the vacant hybrid orbitals on the metal atoms , leading to formation ofσ(C_t→Co) and σ(C_b→{Co_3})bonds. The other typical M-CO bonding is back donation of the lone d-electron pairs on the metal atoms into the carbonyl ligands, forming π(Co→C_t) bonds, σ(Co→{C_(b2)}) bonds and π(Co→{C_(b4)} ) bonds. It is found that there are no direct metalmetal bondings in the skeletons of these two cluster anions.The delocalization situation of the skeletal bonding electrons is briefly discussed.

Quasi-aromaticity in Cluster Chemistry Ⅱ. Localized Molecular Orbital Studies on Co6 （CO）14 ￣（4-） and Ni2Co4 （CO）14 ￣（2-） Cluster Anions

The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co6 （CO）14]￣（4-） and [Ni2Co4 （CO）14]￣（2-）in order to get a deeper insight into the nature of their skeletal bonding. The bonding characteristics of these hexanuclear carbonyl cobaltates are described from a localization bonding viewpoint. There are two typical M-CO bondings, one of which is formed by electron donation from the terminal and capping carbonyl ligands into the vacant hybrid orbitals on the metal atoms , leading to formation ofσ（Ct→Co） and σ（Cb→{Co3}）bonds. The other typical M-CO bonding is back donation of the lone d-electron pairs on the metal atoms into the carbonyl ligands, forming π（Co→Ct） bonds, σ(Co→{Cb2}) bonds and π(Co→{Cb4} ) bonds. It is found that there are no direct metalmetal bondings in the skeletons of these two cluster anions.The delocalization situation of the skeletal bonding electrons is briefly discussed.

31~P NMR Studies on Quasi-Aromaticity of Mo_3S_3 Core and Structure of {Mo_3(μ_3-S)_3[μ-SOP(OEt)_2][S_2P(OEt)_2]_3(CH3CN)}*CH_3CN

The title compound {Mo3 (μ3,-S) (μ-S)3 [μ-SOP (OEt )2] [S2P (OEt)2]3(CH3CN) }. CH3CN, C20H46,Mo3N2O9P4S11, Mr= 1222. 9, has been synthesized bythe reaction of [Mo3 (μ3,-S) (μ-S)3]4+ with Hdtp (hydrogen diethyldithiophosphate)and its structures was dctermined by X-ray crystallography. The crystal data for the title compound: triclinic, P1, Z= 2, a= 13. 011 (8), b= 13. 411 (9), c= 14. 385 (5)A, a=76. 59(5), B=78. 09(5), Y=82. 20(3), V= 2382(2) A3, Dc= 1.705 g/cm3, μ (MoKa) = 1. 434 mm-1, F (000) = 1228. The structure was refined to R =0.080 for 5485 observed reflections. Quasi-aromaticity in the puckered-ring of Mo3S3was experimentally probed by 31p NMR spectroscopic measurements. The 31p chemicalshifts of ligand DTP’s (diethyldithiophosphate) were modulated by the substituent effect of the adjacent bridging aromatic carboxylate through the long-distance super-conjugation via the trinuclear Mo cluster core.

Discovery of the low temperature phase barium metaborate (BBO) and its significance in the search for new type nonlinear optical materials

1 History of discovery of the low temperature phase barium metaborate （BBO）——an excel-lent new-type ultraviolet radiation frequency-doubling crystalline materialTHE first laser excitation in 1960 with ruby （α-Al2O3: Cr） as a laser crystal and the first dou-bling of frequency （347. 15 nm） in 1961 by irradiating quartz crystal （α-SiO2） with a 694. 3nm laser beam have laid the basis for the study of laser and nonlinear optical （NLO） crystals,

Localized molecular orbital studies on B_4C1_4,1,5-C_2B_3H_5 and B_nH_n^(2-)(n = 6-10, 12)

The wave functions, level energies and Mulliken population analysis of localized molecular orbitals (LMO's) for B4Cl4, 1,5-C2B3H5 and the closo-BnHn2- (n = 6-10, 12) are calculated by using the Edmiston-Reudenberg energy localization scheme under the CNDO/2 approximation in order to reveal the nature of quasi-aromaticity of the closo-BnHn2- (n > 5). It has been found that all the B-H or B-Cl LMO's are highly localized between the B and H (or Cl) atoms, corresponding to B-H or B-Cl o-bond, while the Bn framework bonding is formed mainly by the three-centered two-electron B-B-B bonds on the polyhedral faces. In the cases of B4Cl4 and 1,5-C2B3H5, these three-centered B-B-B bonds just fill their polyhedral faces; however, for the framework bonding of the closo-BnHn2- (n > 5), the valence electron deficiency leads to the delocalization of their three-centered B-B-B bonds, and as delocalizability of this three-centered B-B-B bond increases, some three-centered B-B-B bonds are further delocalized to become a four-centered B-B-B-B bond. It is important that for the cioao-BnHn2- (n > 5), the sequence of this delocalizability of the three-centered B-B-B bond is consistent with the degree of quasi-aromaticity of the closo-boranes.