Crystal Structure of Hydrochlorate of 1,1＇-Bis[（4-pyridylamino）carbonyl]ferrocene

The hydrochlorate of 1,1?-bis[(4-pyridylamino)carbonyl]ferrocene (C23H23O3N4ClFe, Mr = 494.75) was structurally characterized by means of X-ray single-crystal diffraction. It crystallizes in triclinic, space group P1 with a = 9.5299(19), b = 12.792(3), c = 9.2644(19) ?, α = 91.56(3), β = 101.97(3), γ = 74.71(3)°, V = 1065.2(4) ?3, Z = 2, Dc = 1.542 g/cm3, F(000) = 512, μ(MoKα) = 0.868 mm-1, T = 291(2) K, the final R = 0.0596 and wR = 0.1531 for 2842 observed reflections with I > 2σ(I). Interestingly, two 1,1?- bis[(4-pyridylamino)carbonyl]ferrocenes (4-BPFA) join shoulder-to-shoulder through intermolecular hydrogen bonds N–H…N, forming an unexpected macrocycle with dimensions of 3.385 ? × 15.778 ?.     

Synthesis,crystal structures,and third-order nonlinear optical properties of a series of ferrocenyl organometallics

Three novel ferrocenyl complexes [Zn(4-PFA)(2)(NO(3))(2)](H(2)O) (1), [Hg(2)(OAc)(4)(4-BPFA)(2)](CH(3)OH) (2), and [Cd(2)(OAc)(4)(4-BPFA)(2)] (3) (4-PFA = [(4-pyridylamino)carbonyl]ferrocene, 4-BPFA = 1,1'-bis[(4-pyridylamino)carbonyl]ferrocene) were prepared, and complexes 1 and 2 were structurally characterized by means of X-ray single-crystal diffraction. In complex 1, the zinc(II) atom is coordinated at a distorted tetrahedral environment by two nitrogen atoms from two 4-PFA moieties and two oxygen atoms from two nitrate anions; [Zn(4-PFA)(2)(NO(3))(2)] units are linked by hydrogen bonds N-H.O and O-H.O forming one-dimensional chains. Complex 2 is a tetranuclear macrocycle compound consisting of two 4-BPFA moieties and two Hg atoms; [Hg(2)(OAc)(4)(4-BPFA)(2)] units form 1-D chains by hydrogen bonds N-H.O as complex 1. Some complexes with 1,1'-bisubstituted pyridine-containing ferrocene ligands have been described, but their crystal data are limited. Compound 2 is the first example of a macrocyclic pyridine-containing ferrocenyl complex. The third-order nonlinear optical (NLO) properties of 4-PFA, 4-BPFA, and complexes 1-3 were determined by Z-scan techniques. The results indicate that all the compounds exhibit strong self-focusing effect. The hyperpolarizability gamma values are calculated to be in the range 1.51 x 10(-)(28) to 3.12 x 10(-)(28) esu. The gamma values are nearly twice as large for complexes 1-3 as for their individual ligands, showing that the optical nonlinearity of the complexes is dominated by the ligands.     

Synthesis and Crystal Structure of a Novel Three-dimensional Supramolecular Compound [（AgI3）（4-HBPFA）2（H2O）]

1 INTRODUCTION In recent years, the rational design and synthesisof metal-directed supramolecular frameworks throughintermolecular hydrogen bonds, π-π stacking interac-tion or other weak interactions have received muchattention because of their interesting molecular topo-logies and various potential applications in catalysis,superconductor, magnetism, nonlinear optics, sen-sors and molecular recognition[1～4]. On the otherhand, the attachment of mono- or polypyridyl frag-ments to a ferr…     

Synthesis and Crystal Structure of (1S)-1,1'-Bis{[N-ethyl-N-(1-methylethyl)-amino]-carbonyl}-2-(hydroxydiphenylmethyl)-ferrocene

The title complex, (1S)-1,1'-bis{[N-ethyl-N-(1-methylethyl)-amino]carbonyl}-2- (hydroxyldiphenylmethyl)-ferrocene ([Fe(C24H22NO2)(C11H16NO)]2·H2O, Mr = 1207.13), was synthesized via (-)-Sparteine-mediated enantioselective directed ortho-lithiation of 1,1'-bis{[N- ethyl-N-(1-methylethyl)-amino]carbonyl}-2-(hydroxydiphenylmethyl)-ferrocene. The structure of the title compound was determined by X-ray single-crystal diffraction. The crystal belongs to the orthorhombic system, space group P212121, with a = 10.26...     

Self-assembled hetero-bimetallic coordination cage and cation-clusters with micro(2)-Cl bridging using a flexible two-arm ferrocene amide linker

One flexible, discrete coordination cage [Cu(2)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(4).4CH(3)OH (), and two cation-clusters with micro(2)-Cl bridging [Ni(2)(micro-Cl)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(3) () and [Co(2)(micro-Cl)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(4).4CH(3)OH (), containing the ferrocenyl functionality were prepared via coordination-driven self-assembly and Cl-anion template from Cu(II), Ni(II) and Co(II) salts and a flexible two-arm molecule 1,1-bis[(3-pyridylamino)carbonyl]ferrocene (3-BPFA).     

Synthesis and catalytic activity of group 5 metal amides with chiral biaryldiamine-based ligands

A new series of group 5 metal amides have been prepared from the reaction between V(NMe(2))(4) or M(NMe(2))(5) (M = Nb, Ta) and chiral ligands, (R)-2,2'-bis(mesitoylamino)-1,1'-binaphthyl (1H(2)), (R)-5,5',6,6',7,7',8,8'-octahydro-2,2'-bis(mesitoylamino)-1,1'-binaphthyl (2H(2)), (R)-6,6'-dimethyl-2,2'-bis(mesitoylamino)-1,1'-biphenyl (3H(2)), (R)-2,2'-bis(mesitylenesulfonylamino)-6,6'-dimethyl-1,1'-biphenyl (4H(2)), (R)-2,2'-bis(diphenylthiophosphoramino)-1,1'-binaphthyl (5H(2)), (R)-2,2'-bis[(3-tert-butyl-2-hydroxybenzylidene)amino]-6,6'-dimethyl-1,1'-biphenyl (6H(2)), (R)-2,2'-bis[(3,5-di-tert-butyl-2-hydroxybenzylidene)amino]-6,6'-dimethyl-1,1'-biphenyl (7H(2)), (R)-2,2'-bis[(3-tert-butyl-2-hydroxybenzylidene)amino]-1,1'-binaphthyl (8H(2)), (S)-2-(mesitoylamino)-2'-(dimethylamino)-1,1'-binaphthyl (9H), and (R)-2-(mesitoylamino)-2'-(dimethylamino)-6,6'-dimethyl-1,1'-biphenyl (10H), which are derived from (R) or (S)-2,2'-diamino-1,1'-binaphthyl, and (R)-2,2'-diamino-6,6'-dimethyl-1,1'-biphenyl, respectively. Treatment of V(NMe(2))(4) or M(NMe(2))(5) (M = Nb, Ta) with 1 equiv of C(2)-symmetric amidate ligands 1H(2), 2H(2), 3H(2), 4H(2), and 5H(2), or Schiff base ligands 6H(2), 7H(2) and 8H(2) at room temperature gives, after recrystallization from a benzene, toluene or n-hexane solution, the vanadium amides (1)V(NMe(2))(2) (11), (2)V(NMe(2))(2) (14), (3)V(NMe(2))(2) (17), (5)V(NMe(2))(2) (22), (6)V(NMe(2))(2) (23) and (7)V(NMe(2))(2) (24), and niobium amides (1)Nb(NMe(2))(3) (12), (2)Nb(NMe(2))(3) (15), (3)Nb(NMe(2))(3) (18), (4)Nb(NMe(2))(3) (20) and [2-(3-Me(3)C-2-O-C(6)H(3)CHN)-2'-(N)-C(20)H(12)][2-(Me(2)N)(2)CH-6-CMe(3)-C(6)H(3)O]NbNMe(2)·C(7)H(8) (25·C(7)H(8)), and tantalum amides (1)Ta(NMe(2))(3) (13), (2)Ta(NMe(2))(3) (16), (3)Ta(NMe(2))(3) (19) and (4)Ta(NMe(2))(3) (21) respectively, in good yields. Reaction of V(NMe(2))(4) or M(NMe(2))(5) (M = Nb, Ta) with 2 equiv of C(1)-symmetric amidate ligands 9H or 10H at room temperature gives, after recrystallization from a toluene or n-hexane solution, the chiral bis-ligated vanadium amides (9)(2)V(NMe(2))(2)·3C(7)H(8) (27·3C(7)H(8)) and (10)V(NMe(2))(2) (28), and chiral bis-ligated metallaaziridine complexes (10)(2)M(NMe(2))(η(2)-CH(2)NMe) (M = Nb (29), Ta (30)) respectively, in good yields. The niobium and tantalum amidate complexes are stable in a toluene solution at or below 160 °C, while the vanadium amidate complexes degrade via diemthylamino group elimination at this temperature. For example, heating the complex (2)V(NMe(2))(2) (14) in toluene at 160 °C for four days leads to the isolation of the complex [(2)V](2)(μ-NMe(2))(2) (26) in 58% yield. These new complexes have been characterized by various spectroscopic techniques, and elemental analyses. The solid-state structures of complexes 12, 13, and 15-30 have further been confirmed by X-ray diffraction analyses. The vanadium amides are active chiral catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, affording cyclic amines in moderate to good yields with good ee values (up to 80%), and the tantalum amides are outstanding chiral catalysts for the hydroaminoalkylation, giving chiral secondary amines in good yields with excellent ee values (up to 93%).     

Building blocks for coordination polymers: self-assembled cleft-like and planar discrete metallo-macrocyclic complexes

Discrete dinuclear metallo-macrocyclic complexes have been prepared from the flexible amide ligand N-6-[(3-pyridylmethylamino)carbonyl]pyridine-2-carboxylic acid (L1-CH(3)), and its more rigid analogue, N-6-[(3-pyridylamino)carbonyl]pyridine-2-carboxylic acid (L3-CH(3)). With ligands L1-CH(3) and L3-CH(3), discrete dinuclear metallo-macrocyclic complexes with the generic formula [Cu(2)(L1-CH(3))(2)(X)(2)(Y)(2)] (7, X = NO(3); 8, X = Cl, Y = H(2)O; 9, X = ClO(4), Y = CH(3)OH) and [Cu(2)(L3-CH(3))(2)(X)(2)(Y)(2)] (10, X = NO(3), Y = H(2)O; 11, X = ClO(4), Y = CH(3)OH) are obtained. For complexes 7-9, containing the more flexible link L1-CH(3), these complexes are cleft-shaped and hinged at the methylene spacer, which allows the cleft to widen and contract to accommodate different packing modes in the solid-state. In contrast, the rigid link L3-CH(3) gives near planar metallo-macrocyclic structures. These metallo-macrocyclic compounds may be useful building blocks for coordination polymers.     

Syntheses and Characterizations of Luminescent Complexes [(BINAP)Pt(C≡CC6H4R-p)2] (R = H, 1; CH3, 2) (BINAP = 2,2''-Bis(diphenylphosphino)-1,1''-binaphthyl)

[(BINAP)Pt(C≡CC6H4R-p)2] (R = H, 1; CH3, 2) (BINAP = 2,2'-bis(diphenylphos- phino)-1,1'-binaphthyl) were synthesized and characterized by X-ray crystallography. Complex 1 crystallizes in triclinic, space group P with a = 11.699(3), b = 12.512(3), c = 15.611(4)(A), α = 93.277(3),β= 97.626(2), γ = 97.375(14)o, V = 2239.9(9)(A)3, Mr = 1014.92, Z = 2, Dc = 1.505 g/cm3, F(000) = 1010, μ(MoKα) = 3.244 mm-1, the final R = 0.0338 and wR = 0.0905 for 7738 observed reflections (I > 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/n with a = 18.03690 (10), b = 13.06060(10), c = 21.6913(3)(A), β= 96.5430(10)o, V = 5076.60(9)(A)3, Mr = 1132.94, Z = 4, Dc = 1.482 g/cm3, F(000) = 2272, μ(MoKα) = 2.973 mm-1, the final R = 0.0481 and wR = 0.0893 for 8916 observed reflections (I > 2σ(I)). Both complexes emit intensively photoluminescence in both solid state and fluid solution due to MLCT (Pt→-C≡CC6H4R-p) emissive state.     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound[Et4N]2[Mo2(CO)8(SC6H4-CH3-p)2]

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｉｎｃｅｔｈｉｏｌａｔｅｌｉｇａｎｄｗａｓｉｎｔｒｏｄｕｃｅｄｉｎｔｏｍｏｌｙｂｄｅｎｕｍｃａｒｂｏｎｙｌｃｏｍｐｏｕｎｄｉｎ1 984 [1],ｔｈｅｉｎｖｅｓｔｉｇａｔｉｏｎｏｎｌｏｗ ｖａｌｅｎｃｅＭｏ -ＳＲｃｏｍｐｏｕｎｄｓｈａｓｒｅｃｅｉｖｅｄａｔｔｅｎｔｉｏｎｆｏｒｔｈｉｓｋｉｎｄｏｆｌｏｗ ｖａｌｅｎｃｅｃｏｍｐｏｕｎｄｓｐｏｓｓｅｓｓｃｅｒｔａｉｎａｄｖａｎｔａｇｅｏｎｃｏｍｐｏｕｎｄｓｙｎ ｔｈｅｓｉｓ,ｍｏｌｅｃｕｌｅｓｔｒｕｃｔｕｒｅａｎｄｐｈｙｓｉｃａｌａ…     

Dual luminescent tetranuclear organogold(I) macrocycles of 5,5'-diethynyl-2,2'-bipyridine and their efficient sensitization of Yb(III) luminescence

Reaction of (AuC≡CbpyC≡CAu)(n) (HC≡CbpyC≡CH = 5,5'-diethynyl-2,2'-bipyridine) with diphosphine ligands Ph(2)P(CH(2))(n)PPh(2) (n = 1 dppm, 3 dppp, 5 dpppen, 6 dpph), 1,1'-bis(diphenylphosphino)ferrocene (dppf), and 1,2-bis(diphenylphosphino)benzene (bdpp) in CH(2)Cl(2) afforded the corresponding dual luminescent gold(I) complexes [(AuC≡CbpyC≡CAu)(2)(μ-dppm)(2)] (1), [(AuC≡CbpyC≡CAu)(2)(μ-dppp)(2)] (2), [(AuC≡CbpyC≡CAu)(2)(μ-dpppen)(2)] (3), [(AuC≡CbpyC≡CAu)(2)(μ-dpph)(2)] (4), [(AuC≡CbpyC≡CAu)(2)(μ-dppf)(2)] (5), and [(AuC≡CbpyC≡CAu)(2)(μ-bdpp)(2)] (6). The solid structures of complexes 1 and 2 are confirmed to be tetranuclear macrocyclic rings by single crystal structure analysis, and those of complexes 3-6 are proposed to be similar to those of complexes 1 and 2 in structure because their good solubility in CH(2)Cl(2), their HRMS results, and the P···P separations of 20.405-20.697 ? in the same linear rigid P-Au-C≡CbpyC≡C-Au-P unit are all favorable to form such 2:4:2 macrocycles. Each of the absorption spectral titrations between complexes 1-6 and Yb(hfac)(3)(H(2)O)(2) (Hhfac = hexafluoroacetylacetone) gives a 2:1 ratio between the Yb(hfac)(3) unit and the complex 1-6 moieties. The energy transfer occurs efficiently from the gold(I) alkynyl antennas 1-6 to Yb(III) centers with the donor ability in the order of 1 ~ 2 ~ 3 ~ 4 > 6 > 5.     

Mixed-transition-metal acetylides: synthesis and characterization of complexes with up to six different transition metals connected by carbon-rich bridging units

The synthesis and reaction chemistry of heteromultimetallic transition-metal complexes by linking diverse metal-complex building blocks with multifunctional carbon-rich alkynyl-, benzene-, and bipyridyl-based bridging units is discussed. In context with this background, the preparation of [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-(PPh(2))C(6)H(3)] (10) (dppf = 1,1'-bis(diphenylphosphino)ferrocene; tBu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl; Ph = phenyl) is described; this complex can react further, leading to the successful synthesis of heterometallic complexes of higher nuclearity. Heterotetrametallic transition-metal compounds were formed when 10 was reacted with [{(eta(5)-C(5)Me(5))RhCl(2)}(2)] (18), [(Et(2)S)(2)PtCl(2)] (20) or [(tht)AuC[triple bond]C-bpy] (24) (Me = methyl; Et = ethyl; tht = tetrahydrothiophene; bpy = 2,2'-bipyridyl-5-yl). Complexes [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)RhCl(2)(eta(5)-C(5)Me(5))}C(6)H(3)] (19), [{1-[(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C]-3-[(tBu(2)bpy)(CO)(3)ReC[triple bond]C]-5-(PPh(2))C(6)H(3)}(2)PtCl(2)] (21), and [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)AuC[triple bond]C-bpy}C(6)H(3)] (25) were thereby obtained in good yield. After a prolonged time in solution, complex 25 undergoes a transmetallation reaction to produce [(tBu(2)bpy)(CO)(3)ReC[triple bond]C-bpy] (26). Moreover, the bipyridyl building block in 25 allowed the synthesis of Fe-Ru-Re-Au-Mo- (28) and Fe-Ru-Re-Au-Cu-Ti-based (30) assemblies on addition of [(nbd)Mo(CO)(4)] (27), (nbd = 1,5-norbornadiene), or [{[Ti](mu-sigma,pi-C[triple bond]CSiMe(3))(2)}Cu(N[triple bond]CMe)][PF(6)] (29) ([Ti] = (eta(5)-C(5)H(4)SiMe(3))(2)Ti) to 25. The identities of 5, 6, 8, 10-12, 14-16, 19, 21, 25, 26, 28, and 30 have been confirmed by elemental analysis and IR, (1)H, (13)C{(1)H}, and (31)P{(1)H} NMR spectroscopy. From selected samples ESI-TOF mass spectra were measured. The solid-state structures of 8, 12, 19 and 26 were additionally solved by single-crystal X-ray structure analysis, confirming the structural assignment made from spectroscopy.     

Enamine Configuration of 5-Methyl-2-phenyl-4-[（Z）-3-tolylamino-phenylmethylene]pyrazol-3（2H）-one

1 INTRODUCTION In contrast to the old-line academic and practical studies of 1-phenyl-3-methyl-4-benzoyl-5-pyrazo- lone (PMBP) on the metal coordination chemistry[1], the complexes of β-ketoamines derivated from PMBP received little attention due to its complicated com- plexation. However, in recent years, there has a sudden growth of this area as a result of its timely interest in biological activities[2]. Recently, a series of β-ketoamines[3] containing PMBP have been prepared fro…     

Metal-metal charge transfer and solvatochromism in cyanomanganese carbonyl complexes of ruthenium and osmium

The complexes [(H3N)5Ru(II)(mu-NC)Mn(I)Lx]2+, prepared from [Ru(OH2)(NH3)5]2+ and [Mn(CN)L(x)] {L(x) = trans-(CO)2{P(OPh)3}(dppm); cis-(CO)2(PR3)(dppm), R = OEt or OPh; (PR3)(NO)(eta-C5H4Me), R = Ph or OPh}, undergo two sequential one-electron oxidations, the first at the ruthenium centre to give [(H3N)5Ru(III)(mu-NC)Mn(I)Lx]3+; the osmium(III) analogues [(H3N)5Os(III)(mu-NC)Mn(I)Lx]3+ were prepared directly from [Os(NH3)5(O3SCF3)]2+ and [Mn(CN)Lx]. Cyclic voltammetry and electronic spectroscopy show that the strong solvatochromism of the trications depends on the hydrogen-bond accepting properties of the solvent. Extensive hydrogen bonding is also observed in the crystal structures of [(H3N)5Ru(III)(mu-NC)Mn(I)(PPh3)(NO)(eta-C5H4Me)][PF6]3.2Me2CO.1.5Et2O, [(H3N)5Ru(III)(mu-NC)Mn(I)(CO)(dppm)2-trans][PF6]3.5Me2CO and [(H3N)5Ru(III)(mu-NC)Mn(I)(CO)2{P(OEt)3}(dppm)-trans][PF6]3.4Me2CO, between the amine groups (the H-bond donors) at the Ru(III) site and the oxygen atoms of solvent molecules or the fluorine atoms of the [PF6]- counterions (the H-bond acceptors).     

The first (ferrocenylmethyl)imidazolium and (ferrocenylmethyl)triazolium room temperature ionic liquids

N-(Ferrocenylmethyl)imidazole (3a), 1-(ferrocenylmethyl)-1,2,4-triazole (3b), 1,1'-bis[(1H-imidazol-1-yl)methyl]ferrocene (8a), 1,1'-bis([1H-(2-methyl)imidazol-1-yl]methyl]ferrocene (8b), and 1,1'-bis[(1H-1,2,4-triazol-1-yl)methyl]ferrocene (8c) were synthesized in moderate yields. These compounds were quaternized with methyl iodide to form 1-(ferrocenylmethyl)-3-methylimidazolium iodide (4a), 1-(ferrocenylmethyl)-4-methyl-1,2,4-triazolium iodide (4b), 1,1'-bis([1-(2,3-dimethyl)imidazolium]methyl)ferrocene diiodide (9b), and 1,1'-bis([1-(4-methyl)-1,2,4-triazolium]methyl)ferrocene diiodide (9c), respectively, in excellent yields. Compounds 4a, 4b, 9b, and 9c were metathesized with bis(trifluoromethanesulfonyl)amide to give high yields of 5a, 5b, 10b, and 10c. With potassium hexafluorophosphate, 9b forms 10d. Salts 5a, 5b, and 10c are the first room-temperature ionic liquids with cations containing an organometallic moiety that exhibit T(g) values well below room temperature, i.e., -32, -16, and -11 degrees C. The compounds were characterized by (1)H, (19)F, and (13)C NMR, MS, and elemental analyses. T(g) values and melting points were determined by DSC. T(d) values (5% weight loss temperature) were recorded by TGA. X-ray single-crystal structures show that 9c and 10d crystallize in the triclinic space group P.     

Spacer-directed coordination polymers-of-oligomers (POLO) of silver

A novel series of Ag(I) polymers-of-oligomers with pyridylcarboxylate spacers supported by a diphosphine [1,1'-bis(diphenylphosphino)methane (dppm) or 1,1'-bis(diphenylphosphino)ferrocene (dppf)] has been constructed and crystallographically established. The repeating oligomeric Ag5 block is invariably made up of five Ag(I) centers comprising Ag2 and Ag units with different metal geometries. Other related Ag5 and Ag4 assemblies have also been isolated. The preparation of the [Ag2(isonic)(dppm)2]n(n+) polymer (isonic = 4-pyridyl formate, NC5H4CO2(-)) using a ligand transfer pathway from NiCl2(dppm) to AgOTf (OTf = CF3SO3(-)) has been identified. The structural outcomes suggested that pyridylcarboxylates of different stereogeometrical and conformational properties can stabilize different oligomeric and topological forms through adaptation to the contrasting demands of the diphosphine and metal.     

Copper(I) complexes of tripodal tris(imidazolyl) ligands: potential mimics of the Cu(A) site of hydroxylase enzymes

Copper(I) complexes of tripodal tris(N-methyl-4,5-diphenyl-imidazolyl)methane ligands, N3CR (1a-c, R = OH, OMe, H), have been prepared as models for the Cu(A) site of copper hydroxylase enzymes. In the absence of additional donors, the ligands 1 react with [Cu(CH3CN)4]PF6 (2) to produce dinuclear complexes [(N3CR)2Cu2](PF6)2 (3) in which the tripodal ligands bridge two trigonal Cu centers; the structures of 3b and 3c are established by X-ray diffraction. Mononuclear adducts [(N3CR)CuL]Z are produced with L = acetonitrile (4), carbon monoxide (5), and t-BuNC (6, 7). The carbonyl complexes 5 are in dynamic equilibrium with the dimeric complexes 3, but 5c (R = H) can be isolated. The structures of the isocyanide derivatives depend critically on the tripod methane substituent, R. Thus, the X-ray structures of 6 (R = OMe) and 7 (R = H) show trigonal and tetrahedral geometries, respectively, with bi- or tridentate coordination of the tripod. A trinuclear complex [Cu3(N3COH)2(t-BuNC)2](PF6)3 (8) is formed from N3COH (1a) which features both three-coordinate and two-coordinate Cu atoms and bidentate tripod coordination. Reactions of dioxygen with dinuclear 3c or mononuclear [(N3CR)CuL]Z are sluggish, producing from the latter in acetone [(N3CH)CuII(L)(L')](PF6)2 (9, L = acetone, L' = H2O).     

Unusual reactions of [{micro-(phthalazine-N2:N3)}Fe2(micro-CO)(CO)6] with organolithium reagents. A novel coordination mode of 1,2-diazane diiron carbonyl compounds

[{Micro-(phthalazine-N2:N3)}Fe2(micro-CO)(CO)6](1) reacts with organolithium reagents, RLi (R = CH3, C6H5, p-CH3C6H4, p-CH3OC6H4, p-CF3C6H4, p-C6H5C6H4), followed by treatment with Me3SiCl to give the novel diiron carbonyl complexes with a saturated N-N six-membered diazane ring ligand, [{C6H4CH(R)NNCH2}Fe2(C=O)(CO)6](2, R = CH3; 3, R = C6H5; 4, R =p-CH3C6H4; 5, R =p-CH3OC6H4; 6, R =p-CF3C6H4; 7, R =p-C6H5C6H4). Compounds 4 and 5 were treated with [(NH4)2Ce(NO3)6] to afford the aryl-substituted phthalazine-coordinated diiron carbonyl compounds [(micro-{1-(p-CH3C6H4)-phthalazine-N2:N3})Fe2(micro-CO)(CO)6](8) and [(micro-{1-(p-CH3OC6H4)-phthalazine-N2:N3})Fe2(micro-CO)(CO)6](9), respectively. The structures of complexes 4 and 9 have been established by X-ray diffraction studies.     

Crystallographic Characterization of the Novel Inorganic-organic Hybrid Coordinated Polymer:[(C22H50N2)(Ag2I4)]n

1 INTRODUCTION Halometallates are the particularly suitable systems for designing the construction of unusual low-dimensional structural archetypes, from which peculiar electronic, thermal, catalytic and magnetic properties can arise. The syntheses of th…     

Synthesis and Crystal Structure of E-4,4’-Bis(N,N-di-n-butylamino)stilbene

1 INTRODUCTION Two-photon absorption is a subject which attracts fast-growing interest in chemistry, photonics, and biological imaging fields in the past decades[1]. The two-photon techniques have wide applications, for example, optical power limiting[2], two-photon opti- cal memory[3], two-photon confocal imaging[4] and up-conversion laser[5]. Especially recently, the inte- rest has gradually been focused on studying two- photon initiated photopolymerization (TPIP) and exploring some pe…     

Alkali-metal-mediated manganationII of functionalized arenes and applications of ortho-manganated products in Pd-catalyzed cross-coupling reactions with iodobenzene

Extending the recently introduced concept of "alkali-metal-mediated manganation" to functionalised arenes, the heteroleptic sodium manganate reagent [(tmeda)Na(tmp)(R)Mn(tmp)] (1; TMEDA=N,N,N',N'-tetramethylethylenediamine, TMP=2,2,6,6-tetramethylpiperidide, R=CH2SiMe3) has been treated with anisole or N,N-diisopropylbenzamide in a 1:1 stoichiometry in hexane. These reactions afforded the crystalline products [(tmeda)Na(tmp)(o-C6H4OMe)Mn(tmp)] (2) and [(tmeda)Na(tmp){o-{C(O)N(iPr)2C6H4}Mn(CH2SiMe3] (3), respectively, as determined from X-ray crystallographic studies. On the basis of these products, it can be surmised that reagent 1 has acted, at least partially and ultimately, as an alkyl base in the first reaction liberating the silane Me4Si, but as an amido base in the second reaction liberating the amine TMPH. Both of these paramagnetic products 2 and 3 have contacted ion-pair structures, the key features of which are six-atom, five-element (NaNMnCCO) and seven-atom, five-element (NaNMnCCCO) rings, respectively. Manganates 2 and 3 were successfully cross-coupled with iodobenzene under [PdCl(2)(dppf)] (dppf=1,1'-bis(diphenylphosphino)ferrocene) catalysis to generate unsymmetrical biaryl compounds in yields of 98.0 and 66.2 %, respectively. Emphasizing the importance of alkali-metal mediation in these manganation reactions, the bisalkyl Mn reagent on its own fails to metalate the said benzamide, but instead produces the monomeric, donor-acceptor complex [Mn(R)2{(iPr)2-NC(Ph)(==O)}2] (5), which has also been crystallographically characterised. During one attempt to repeat the synthesis of 2, the butoxide-contaminated complex [{(tmeda)Na(R)(OBu)(o-C6H4OMe)Mn}2] (6) was obtained. In contrast to 2 and 3, due to reduced steric constraints, this complex adopts a dimeric arrangement in the crystal, the centrepiece of which is a twelve atom (NaOCCMnC)2 ring.