Yong-Jin Xu

Cobalt complexes with pnicogen (phosphine or pyridine) and thiolato ligands. Syntheses, X-ray crystal structures and spectroscopic characterization

Abstract Mixed pnicogen and thiolato mononuclear cobalt complexes, Co(SR)2(PBun3)2 [R = Ph (1); R = Stolyl-p (2)] and Co(mpo)2L [L = PBun3 (3); L = Py (4)], have been synthesized and studied spectroscopically. The complexes 1 and 2 are tetrahedral, as determined by magnetic susceptibility studies. The structures of 3 and 4 were determined by X-ray diffraction. The cobalt(II) ions in both 3 and 4 are in a square-pyramidal environment with the two trans-oriented mpo ligands in the basal plane and the pnicogen group in the axial position.

Cobalt (iron) thiolato complexes containing the Co-ligand phosphine and reaction products of the structural fragment ML 2 L? (L = 1,2-bidentate thiolate,L?= tertiary phosphine)

Mono-, di-, tri-, and tetra-nuclear cobalt (iron) complexes containing co-ligands phosphine and thiolate are presented according to the classification by combination of different dentates of the two ligands. Emphasis is being put on the triand tetranuclear cluster complexes of monodentate phosphines and 1,2-bidentate thiolates. These complexes are considered to be constructed based on the general structural fragment (or building block) ML2L′ (L=1,2-bidentate thiolate,L′=tertiary phosphine). Structural regularities are presented in Tables I, III, IV, and V and discussed. FAB mass spectroscopic data showed the possible fragmentation patterns. Synergism of the cluster skeletons is proposed to explain the occurrence of the distinct structural modes.

Synthesis and crystal structures of two dichloro-bridged dimeric metal complexes of 1,4,7-triazacyclodecane: [Zn2(tacd)2Cl2 [Cu2(tacd)2Cl2](ClO4)2

Abstract Two dichloro-bridged dimeric metal complexes of 1,4,7-triazacyclodecane (tacd), [Zn 2 (tacd) 2 Cl 2 ](ClO 4 ) 2 ( 1 ) and [Cu 2 (tacd) 2 Cl 2 ](ClO 4 ) 2 ( 2 ) ( 2 ), have been prepared and characterized by X-ray crystallography. Each zinc (II) atom in 1 is surrounded by a distorted trigonal-bipyramidal N 3 Cl 2 environment with ZnN and ZnCl bond lengths at ranges of 2.038 (5) to 2.114 (4) A and 2.292 (1) to 2.715 (2) A, respectively. Each copper (II) atom in 2 adopts a highly distorted trigonal-bipyramidal N 3 Cl 2 coordination geometry with the CuN and CuCl bond lengths at ranges of 2.011(4) to 2.180(4) A and 2.323(3) to 2.353(1) A, respectively.

A novel asymmetrical phosphine tetracobalt complex ofo-Mercaptophenol: Synthesis, structure, and properties of Co4mp4(Hmp)(PBu 3 n )3 (H2mp=o-Mercaptophenol)

AbstractComplex Co4mp4(Hmp)(PBu3n)3 (1) (H2mp=o-Mercaptophenol) was obtained from the reaction of CoCl2 and H2mp in the presence of PBun3 and NaOMe with restricted oxidation. X-ray crystallographic data: triclinic, space group

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF A METHOXIDEBRIDGED BINUCLEAR MANGANESE(III) COMPLEX WITH BIS(2-OXYPHENYL)DISULFIDE (MP-MP2); Mn2 (μ-OCH3)2(MP-MP)2(DMSO)2

P - \overline 1

Phosphine-Participated Cluster Formation: Syntheses, Structures, and Magnetic Properties of Tri- and Tetracobalt Phosphine Complexes of o-Mercaptophenol (H2mp), Co3(mp)2(Hmp)2(PEt3)3 and Co4(mp)4(PBun3)3Cl(MeOH)

,a=15.657(5) Å,b=20.469(8) Å,c=12.383(3) Å,α=93.59(3)°, β=112.45(2)°, γ=93.65(3)°,V=3648.7 Å3,Z=2,Dc=1.33 g/cm3;R=0.065. The molecule consists of four cobalt atoms unsymmetrically bridged by S or S and O atoms from four of the five mp ligands. The fifth mp is terminally chelated to Co(4) which is in a distorted trigonal bipyramidal geometry, while Co(1)-Co(3) are square pyramidal. Atom Co(2) is bonded to Co(1) and Co(3) (average distance 2.632 Å) with strong interactions while Co(4) is only loosely connected to Co(1) (3.402 Å) and Co(3) (2.956 Å) through oxygen bridges and a hydrogen bond. The different coordination environments O2S2P, S4P, and O4S of the cobalt atoms make the molecule highly asymmetrical. XPS fitting data confirm the difference of the Co atoms. FABMS data indicate the possible fragmentation routes. The complex is paramagnetic with μeff=5.2 μB.

Structural comparison to the molybdenum site of nitrogenase. Synthesis and crystal structure of binuclear oxomolybdenum(V) complex with both o‐mercaptophenolate and alkoxide ligands

Abstract Complexes [A][Mo 2 O 2 (μ-O)mp 3 Na(EtOH) 3 ] (A = Et 4 N (1a); A = nBu 4 N (1b)) and (n-Bu 4 N) [Mo 2 O 2 (μ-OEt)mp 3 ] (2) have been obtained by the reaction of MoOCl 3 (THF) 2 and Na 2 mp (H 2 mp = o -mercaptophenol) in appropriate solvents. Both (1b) and (2) crystallize in monoclinic space group P2 1 /n. Cell parameters for (1b): a = 12.776(3), b = 14.154(5), c = 26.281(7) A, β = 95.50(2)°, V = 4730.5 A 3 , Z = 4, D calc = 1.427 g/cm 3 ; for (2): a = 12.617(5), b = 23.817(18), c = 14.228(7) A, β = 105.79(4)°, V = 4114.1 A 3 , Z = 4, D calc = 1.427 g/cm 3 . The structures were solved by direct methods from 3348 (1b) or 1583 (2) unique reflections with I > 3σ (I) to final convergence factors of R(R w ) 0.070(0.070) for (1b) and 0.090(0.099) for (2). The two [Mo(O)mp] + units are triply bridged by one doubly bridging mp 2− ligand with exceedingly small bite angles (68.85°) and bite distances (2.70 A) and an inorganic oxygen atom for (1b) or an ethoxy group for (2). The molybdenum(V) atoms are in an environment of O 4 S 2 , forming a distorted octahedron with the terminal oxo groups cis to each other. Information concerning the possible origin of oxygen atoms in MoFepr is derived from the structural data of these two complexes. 1 H NMR and CV measurements were also studied.

A novel mixed-coordination cobalt(III)complex:synthesis and structure of Co(III)(mpp)(Hmpp)(n-Bu3P)2

Abstract The title complex Mn2 (μ-OCH3)2(MP-MP)2(DMSO)2 1, (MP-MP2- = bis(2-oxyphenyl)disulfide) was obtained by the reaction of Mn(CH3CO2)2.4H2O, H2MP (o-mercaptophenol) and NaOMe in the mixed solvent DMSO/CH3OH. The structure of 1 was determined by X-ray diffraction methods. Crystal data: C30H34Mn2O8S6, triclinic, P 1, a = 8.410(1), b = 8.738(1), c = 12.588 (2)A, a = 82.85(1), β = 85.78(1), y = 72.38(1)°, V = 874.1 A3,Z = 1, Mr = 824.86, dx = 1.57 g/cm3, F(000) = 424, μ (Mo Kα) = 10.8 cm−1, R(Rw ) = 0.057(0.061). The molecule consists of two monomers, Mn(OCH3)(MP-MP)(DMSO), bridged by the methoxide groups. Each MP-MP2- ligand provides two phenolate oxygen atoms and one disulfide sulfur atom to the manganese(III) ion in the Mn2(μ-OMe)2 unit. The effective magnetic moment is μeff = 4.24 μB per Mn(III) ion at room temperature.