Ben-Jie Liaw

A 2D honeycomb-shaped network based on a starburst cluster: [Ag4(μ3-Cl)(PPh2(CH2)2PPh2)1.5{S2P(OR)2}3](R = Et, Pri)

The first 2D metal-organic framework utilizing PPh2(CH2)2PPh2 (dppe) units as the linkers and tetranuclear silver clusters, [Ag4(micro3)-Cl){S2P(OR)2}3], as the network nodes in the formation of the honeycomb-shaped layer structure is reported.

Coordination chemistry of Group 12 metals with phosphorodiselenoates: syntheses, structures and VT 31P NMR study of monomer–dimer exchange equilibrium

The reactions of diselenophosphates, [dsep, (RO)2PSe2-; R = Et, (n)Pr and (i)Pr] with cadmium(II) and mercury(II) perchlorates in a 2 : 1 molar ratio formed compounds of stoichiometry M[Se2P(OR)2]2{M = Cd, R = Et (1), (n)Pr (2), (i)Pr (3); Hg, Et(4), (n)Pr (5), (i)Pr (6)}, and with zinc(II) perchlorates, chalcogen centered tetranuclear clusters, [Zn4(micro4-E){Se2P(OR)2}6]{E = Se, R = Et (7), (n)Pr (8), (i)Pr (9); E = O, R = Et (10), (n)Pr (11), (i)Pr (12)} were formed. All these complexes have been characterized with the help of analytical data, X-ray crystallography (1, 3, 6, 10, 11 and 12), and FAB-mass spectrometry (7-12). Compound 1 is a linear double-chain polymer, in which each pair of Cd atoms is bridged by two dsep ligands; the mercury 6 polymer has a helical chain structure, in which two Hg atoms are bridged by one dsep ligand, and the other ligand chelates the Hg atom. The chelating dsep ligands lie on either side of the helical chain. Compound 3 exists as a dimer in which two cadmium atoms are connected by two bridging dsep ligands, and each cadmium atom is further chelated by a dsep ligand. The metal atoms in 1, 3 and 6 are each coordinated by four selenium atoms in a distorted tetrahedral geometry. Clusters 10-12 have tetrahedral array of zinc atoms with an oxygen atom in the center with edge-bridging dsep ligands. Positive FAB-mass spectra support the formation of selenium-centered clusters,7-9, of which the cluster 8 was structurally confirmed earlier. The solution state behavior of compounds 1-12 has been studied by using multinuclear NMR spectroscopy. Dimer 3 in CD2Cl2 showed monomer-dimer exchange equilibrium in the temperature range 20 to -90 degrees C and the free energy of activation is calculated from the coalescence temperature as DeltaG++(223 K)= 38.5 kJ mol(-1). Polymer undergoes depolymerization in CDCl3 and exhibits monomer-dimer exchange equilibrium in the temperature range 20 to -60 degrees C.

Dithiolate clusters of copper(I): utilization of all possible coordination sites of 1-(diethoxyphosphinyl)-1-cyanoethylene-2,2-dithiolate

Four CuI–S clusters, 1–4, containing bridging dppm and 2-(diethoxyphosphinyl)-2-cyanoethylene-1,1-dithiolato ligands were isolated from the reaction of [Cu2(μ-dppm)2(CH3CN)2](PF6)2 and K2S2CC(CN)P(O)(OEt)2 in CH2Cl2. The cluster nuclearity depends on the coordination pattern of the functionalized 1,1-dithiolates: 1 and 2, Cu4(dppm)4[S2CC(CN)P(O)(OEt)2]2 and Cu4(dppm)3(OPPh2CH2PPh2)[S2CC(CN)P(O)(OEt)2]2, display a tetrametallic tetraconnective (μ-S, μ-S) bridging mode; in 3, Cu5(dppm)4[S2CC(CN)P(O)(OEt)2]2(PF6), exhibits a novel tetrametallic pentaconnective coordination pattern; in 4, Cu9(dppm)4[S2CC(CN)P(O)(OEt)2]4(PF6), reveals an unprecedented pentametallic hexaconnective coordination pattern. Pertinent crystallographic data are: 1, C114H108Cu4N2O6P10S4·CH2Cl2, monoclinic, P21/n, a = 20.1464(11), b = 23.4222(13), c = 23.7695(14) A, β = 91.837(1)°, V = 11210(1) A3, Z = 4; 2, C114H108Cu4N2O7P10S4, monoclinic, P21/n, a = 15.6463(8), b = 52.324(3), c = 15.8286(8) A, β = 118.529(1)°, V = 11385(1) A3, Z = 4; 3, C114H116Cu5F6N2O10P11S4, monoclinic, C2/c, a = 20.4306(11), b = 22.6378(12), c = 26.1927(13) A, β = 90.886(1)°, V = 12112.8(11) A3, Z = 4; 4, C128H128Cu9F6N4O12P13S8, orthorhombic, Pna21, a = 38.8644(11), b = 24.3585(8), c = 16.0870(5) A, V = 15229.2(8) A3, Z = 4.

Ag8Cl2[Se2P(OEt)2]6: A rare example containing a combination of discrete clusters and chains

The novel halide-centered Ag(I)8 cubic clusters containing diethyl diselenophosphato ligands are prepared and their solid state structures, a discrete unit or a one-dimensional chain, are dictated by the counter anions.