Shan-Ming Kuang

Synthesis of Fe-M complexes (M = Mo, Mn, Fe, Co, Ni, Zn, Cd, Hg) using trans-Fe(EtPhPpy)2(CO)3 as an organometallic tridentate ligand molecular structures of (CO)3Fe(μ-EtPhPpy)2Mo(CO)3 and (CO)3Fe(μ-EtPhPpy)2Cd(SCN)2 (EtPhPpy = 2-(ethylphenylphosphino)pyridine)

Abstract trans -Fe(EtPhPpy) 2 (CO) 3 reacts with Mo(CO) 6 and M(SCN) 2 (M = Mn, Fe, Co, Ni, Zn, Cd, Hg) to form binuclear complexes containing an Fe-M bond. Crystal and molecular structures of the title complexes have been determined by X-ray analysis, which yielded Fe(0)-Mo(0) and Fe(0)-Cd(II) bonded lengths of 2.922(1) A and 2.648(1) A respectively.

Synthesis and structural characterization of binuclear silver(I) complexes bridged by three polydentate phosphine ligands

Abstract The reaction of AgNO 3 with 3,6-bis(diphenylphosphino)pyradazine, L 1 , in the ratio of 2:3 in dichloromethane afforded the new binuclear complex [Ag 2 (μ-L 1 ) 3 (η 2 -NO 3 ) 2 ] ( 1 ), while the reaction of AgClO 4 with 2,6-bis(diphenylphosphino)pyridine, L 2 , in the ratio of 2:3 in dichloromethane afforded [Ag 2 (μ-L 2 ) 3 ](ClO 4 ) 2 ( 2 ). The reaction of [Ag 2 (μ-L 3 ) 2 (MeCN) 2 ](ClO 4 ) 2 (L 3 xa0=xa0(2-diphenylphosphino-6-pyrazol-1-yl)pyridine) with dppm gave the ligand substitution product [Ag 2 (μ-L 3 ) 2 (μ-dppm)](ClO 4 ) 2 ( 3 ), in high yield. The structures of all three compounds have been determined by single crystal X-ray analysis.

Binuclear complexes containing an iron(I)-mercury(I) bond from oxidation of trans-[Fe(CO)2(CS2)(Ph2Ppy-P)2] with HgX2 (Ph2Ppy = 2-(diphenylphosphino) pyridine, X = Cl, SCN)

Abstract trans-[Fe(CO)2(CS2)(Ph2Ppy-P)2] reacts with HgX2 (X = Cl, SCN) in dichloromethane at room temperature to give heterodinuclear complexes XFe(CO)2(μ-Ph2Ppy)2HgX (X = SCN, 1; X = Cl, 2) containing an iron(I)-mercury(I) bond. The Fe(I)-Hg(I) bond length as determined by X-ray analysis is 2.527(2) A for 1 and 2.529(1) A for 2.

The first seven-coordinated iron(II) complex with a nitrogen donor set hepta-dentate macrocyclic polyamine ligand and different coordination modes with its cobalt(II) analogue

Abstract The Fe2+ and Co2+ complexes with a hepta-dentate ligand, 1-methyl-4,7,10-tris(2-pyridylmethyl)-1,4,7,10-tetraazacyclododecane (L), have been synthesized and their crystal structures determined by X-ray diffraction analyses. The two complexes have been found to have different coordination modes. The Fe2+ complex (I) is seven-coordinated with the four cyclen (cyclen=1,4,7,10-tetraazacyclododecane) nitrogen donors and all three pendant pyridine nitrogens, adopting a mono-capped distorted octahedral coordination geometry. To our knowledge, this is the first example of a structurally characterized seven-coordinated Fe2+ complex formed with only one N7 donor set ligand. Whereas the Co2+ complex (II) of L is a normal six-coordination with four cyclen nitrogen donors and two pendant pyridines to give a distorted octahedron in which one pendant pyridine nitrogen remains uncoordinated.

Reaction of M(CO)Cl(L)2 with mercury(II) chloride (M = Ir, Rh; L = Ph2Ppy, P(fur)3) (Ph2Ppy = 2-(diphenylphospino)pyridine, P(fur)3 = tri-(2-furyl)phosphine)

Abstract Reaction of Ir(CO)Cl(Ph2Ppy)2 with mercury(II) chloride gave Ir(CO)Cl2(μ-Ph2Ppy)2HgCl (1), as the main product and Ir2(CO)2Cl4(μ-Ph2Ppy)2 (2), as the by-product, whereas reaction of Ir(CO)Cl{P(fur)3}2 with mercury(II) chloride only gave Ir(CO)Cl2{P(fur)3}2HgCl (3). Reaction of Rh(CO)Cl(L)2 with mercury(II) chloride gave Rh(CO)Cl2(μ-L)2HgCl (Lxa0=xa0Ph2Ppy (4); Lxa0=xa0P(fur)3 (5)). The crystal and molecular structures of 2·CH2Cl2, 4·1/2H2O and 5 have been determined by X-ray analysis.

Reaction of [Cu2(μ-Ph2Ppypz)2(MeCN)2](ClO4)2 (Ph2Ppypz=(2-diphenylphosphino-6-pyrazol-1-yl)pyridine) with Fe(CO)42− and X− (X=Cl, I, MeCO2 and pyrazolate)

Abstract [Cu 2 ( μ -Ph 2 Ppypz) 2 (MeCN) 2 ](ClO 4 ) 2 (Ph 2 Ppypz=(2-diphenylphosphino-6-pyrazol-1-yl)pyridine) reacts with Fe(CO) 4 2− in tetrahydrofuran to give [Cu 2 ( μ -Ph 2 Ppypz) 2 (MeCN) 2 ](Fe(CO) 4 ), 1, and with X − in acetonitrile or tetrahydrofuran at room temperature to afford [Cu 2 ( μ -Ph 2 Ppypz) 2 ( μ -X)](ClO 4 ) (X=Cl, 2 ; I, 3 ; MeCO 2 , 4 ; pyrazolate, 5 ). The crystal structures of 1 , 3 ·Et 2 O, 4 ·Et 2 O and 5 have been determined by X-ray crystallography.

Directional Fe–CO⋯S intermolecular interaction leading to chain-like crystal packing in binuclear Fe(0)–M(II) (M=Hg, Cd) complexes with 2-(diphenylphosphino)thiazole

Abstract A new thiazole-based phosphine ligand was designed to construct heterobinuclear complexes (CO) 3 Fe( μ -Ph 2 PNS) 2 MX 2 (M=Hg, X=SCN; M=Cd, X=I; Ph 2 PNS=2-(diphenylphosphino)thiazole), in which weak Fe–Cue606O⋯S intermolecular interaction led to chain-like molecular packing in the solid state.

Metal–metal bond cleavage in the trinuclear clusters M3(CO)12-n(Ph2Ppy)n (M=Ru, n=3; Os, n=1; Ph2Ppy=2-(diphenylphosphino)pyridine) by Lewis acids

Abstract Reaction of M 3 (CO) 12- n (Ph 2 Ppy) n (M=Ru, n =3; M=Os, n =1) with HgX 2 (X=Br, Cl) gave cis -M(CO) 3 ( μ -Ph 2 Ppy)(HgX) 2 , (M=Ru, 1 ; M=Os, 2 ), and the reaction of Ru 3 (CO) 9 (Ph 2 Ppy) 3 with CdI 2 resulted in the formation of I(CO) 2 Ru( μ -Ph 2 Ppy) 2 Ru(CO) 2 I, 3, which demonstrate the cleavage of metal-metal bonds by Lewis acids. The crystal and molecular structures of 1 , 2 and 3· 0.5MeOH·H 2 O have been determined by X-ray analysis.

Reaction of 2-(diphenylphosphino)-pyridine and -thiazole organoiron(0) polydentate ligands with iron(III) salts: X-ray structures of [η2-Ph2P(O)py]2Fe(μ-Cl)2FeCl2 and Fe(NCS)2[η2-Ph2P(O)taz]2 (taz=thiazole)

Abstract The reaction of trans -Fe(CO) 2 (CS 2 )(Ph 2 Ppy- P ) 2 (Ph 2 Ppy=2-(diphenylphosphino)pyridine) with FeCl 3 resulted in the formation of the binuclear complex [η 2 -Ph 2 P(O)py] 2 Fe(μ-Cl) 2 FeCl 2 ( 1 ), while the reaction of trans -Fe(CO) 3 (Ph 2 Ptaz- P ) 2 (Ph 2 Ptaz=2-(diphenylphosphino)thiazole) with Fe(NCS) 3 gave Fe(NCS) 2 [η 2 -Ph 2 P(O)taz] 2 ( 2 ). The crystal structures of ( 1 ) and ( 2 )·C 6 H 6 have been determined using X-ray crystallography.

Formation of donor–acceptor Fe(0)–Hg(II) bond in separation and stabilization of optically active iron(0) phosphine complexes. Absolute configuration of (+)-(R)-(CO)4Fe(μ-EtPhPpy)HgCl2

The chiral phosphine ligand 2-(ethylphenylphosphino)pyridine (EtPhPpy, R / S mixture) reacts with Fe(CO) 5 to give racemic (±)-Fe(CO) 4 (EtPhPpy- P ), which undergoes an addition reaction with HgCl 2 to afford the optically active binuclear Fe(0)–Hg(II) complexes (+)-( R )-(CO) 4 Fe(μ-EtPhPpy)HgCl 2 and (−)-( S )-(CO) 4 Fe(μ-EtPhPpy)HgCl 2 , which can be separated manually in crystalline form. The absolute configuration of (+)-( R )-(CO) 4 Fe(μ-EtPhPpy)HgCl 2 has been determined by single crystal X-ray analysis.