One-Pot Regioselective Synthesis of Spiroimidazolidinones via a Sequential Ugi 4CR/Azide-Isocyanide Coupling/Cyclization/Rearrangement/Hydroxylation Reaction.

Herein a novel and robust methodology to spiroimidazolidinones has been developed under a mild reaction. The reaction of (Z)-2-azido-3-phenylacrylic acids , aldehydes , amines , isocyanides , and isocyanides produced regioselectively spiroimidazolidinones in 71-88% yields via a sequential Ugi 4CR/Pd(0) catalyzed azide-isocyanide coupling/cyclization/rearrangement/hydroxylation reaction. Furthermore, the easily accessible starting materials, high bond-forming efficiency, and broad substituent tolerance make this strategy useful in synthetic and medicinal chemistry.

Multifunctional Optimization of MXene for Enhanced Comprehensive Performance of Crystal Silicon-MXene Back-Heterojunction Solar Cells.

Enhancing the cost-performance ratio is a fundamental objective for the advancement of the photovoltaic sector. In this context, the development of innovative solar cells that offer a straightforward device configuration but high performance is arguably the most crucial element. Herein, an undoped back-heterojunction crystalline silicon (c-Si) solar cell is endeavored to be crafted by simply drop-casting a TiCT MXene ethanol colloidal solution onto the backside of an n-type c-Si (n-Si) wafer.

One-Stone-for-Multiple-Birds Additive Strategy for Highly Efficient and Stable Carbon-Based Hole-Transport-Layer-Free CsPbIBr Solar Cells.

During fabrication and operation of perovskite solar cells (PSCs), defects commonly arise within the crystals as well as at grain boundaries. However, conventional additive strategies typically only serve to mitigate the occurrence of a single defect and fail to significantly enhance device performance. Herein, carbon-based hole-transport-layer-free CsPbIBr devices are focused on, one kind of important PSCs with more stable structure and an appropriate bandgap for a semitransparent solar cell or a top cell in a tandem configuration, and present a highly efficient one-stone-for-multiple-birds additive strategy based on lanthanide trifluoromethanesulfonates (Ln(OTF), Ln: neodymium (Nd), europium (Eu), dysprosium (Dy), thulium (Tm)).

Insight into the anti-proliferation activity and photoinduced NO release of four nitrosylruthenium isomeric complexes and their HSA complex adducts.

Four Ru(II)-centered isomeric complexes [RuCl(5cqn)(Val)(NO)] (1-4) were synthesized with 5cqn (5-chloro-8-hydroxyquinoline) and chiral Val (Val = L- or D-valine) as co-ligand, and their structures were confirmed using the X-ray diffraction method. The cytotoxicity and photodynamic activity of the isomeric complexes and their human serum albumin (HSA) complex adducts were evaluated. Both the isomeric complexes and their HSA complex adducts significantly affected HeLa cell proliferation, with an IC50 value in the range of 0.

Coordination reactions of 2-pyridinecarboxaldehyde-phenylhydrazonatolithium with selected transition metal (Zn, Sn, Fe, Co, Ni and Zr) chlorides and its coupling reaction with dichloromethane.

The reactions of 2-pyridinecarboxaldehyde-phenylhydrazonatolithium C5H4Npy-CH[double bond, length as m-dash]Ni-NaLi(Ph) (abbreviated as Li) with a 1/2 equivalent of anhydrous metal (Zn, Sn, Fe and Co) chlorides or NiCl2(DME) (DME = 1, 2-dimethoxyethane) produced the corresponding mononuclear metal(ii) complexes ( and ), in which each ligand acts as a bidentate ligand and the coordination geometries around the metals are shown to be tetrahedral within the complexes , , and , respectively, and a tetragonal pyramid in the complex . The reaction of Li successively with sodium tert-butoxide and anhydrous ZrCl4 afforded the unanticipated bizirconium complex , in which each monoanionic ligand behaves as a tridentate bridge. Whereas treatment of Li with NiCl2 and then CH2Cl2 led to an interesting methylene-bridged bis(2-pyridyl-phenylhydrazone) compound in moderate yield; a comparative experiment showed that when the Li reacted with CH2Cl2, the coupling compound was also obtained but in very low yield.

Crystal structure of [1-(2,6-diiso-propyl-phen-yl)-2,4-bis-(di-methyl-amino)-5-tri-methyl-silyl-1,3,5-tri-aza-penta-dienyl-κ(2) N (1),N (5)](tri-phenyl-phosphane-κP)copper(I).

The title complex, [Cu(C21H38N5Si)(C18H15P)], was obtained from the one-pot reaction between (Dipp)N(Li)SiMe3 (Dipp = 2,6-diiso-propyl-phen-yl), Me2NCN, CuCl and PPh3. The Cu(I) atom has a distorted trigonal-planar coordination sphere. The tri-aza-penta-dienyl ligand acts as a κ(2)-donor.

A white phosphorescent coordination polymer with Cu2I2 alternating units linked by benzo-18-crown-6.

A new approach has been illustrated for the development of stable, efficient, and environmentally "friendly" white phosphorescent materials. Under mild conditions, a new one-dimensional coordination polymer has been prepared from benzo-18-crown-6 with CuI in the presence of KI, which is capable of emitting direct white light in the solid state.

catena-Poly[[(N,N-di-methyl-cyanamide-κN)lithium]-μ3-bromido].

The title complex, [LiBr(C3H6N2)] n , is the unexpected product of a reaction beteween (Dipp)N(Li)SiMe3 (Dipp = 2,6-diiso-propyl-phen-yl), Me2NCN and CuBr. The compound is a one-dimensional polymer with a step structure derived from the association of inversion dimers, formed by bromido ligands bridging two Li(+) cations, each of which carries a di-methyl-cyanamide ligand. The planar (LiBr)2 unit of the polymer core has a regular rhombic shape [Li-Br-Li 77.

Metal (Mg, Fe, Co, Zr and Ti) complexes derived from aminosilyl substituted aminopyridinato ligand: synthesis, structures and ethylene polymerization behaviors of the group 4 complexes.

Lithium N-[(N,N-dimethylamino)dimethylsilyl]-2-pyridylamidate (2) was prepared from the reaction of new compound N-[(N,N-dimethylamino)dimethylsilyl]-2-pyridylamine (1) and LiBu(n). Treatment of the lithium salt (2) with an equal equivalent of MgBr(2)(THF)(2), FeCl(2) and CoCl(2) afforded the corresponding dinuclear complexes , , and , in which metal atoms possess similar trigonal bipyramidal geometries and each ligand functions as a bimetallic bridging binding aminopyridinato moiety with N-donation from the dimethylamino group. While the stoichiometric reaction of with ZrCl(4) gave the mononuclear zirconium complex (6); the seven coordinated zirconium atom adopts a distorted pentagonal bipyramid geometry and the ligand acts as monoanionic η(2)-aminopyridinato moiety with the pendant arm coordinated via N(CH(3))(2).

meso-Bis{η(5)-1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienyl}iron(II) and the cobalt(II) analogue.

The two title crystalline compounds, viz. meso-bis{η(5)-1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienyl}iron(II), [Fe(C(12)H(20)NSi)(2)], (II), and meso-bis{η(5)-1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienyl}cobalt(II), [Co(C(12)H(20)NSi)(2)], (III), were obtained by the reaction of lithium 1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienide with FeCl(2) and CoCl(2), respectively. For (II), the trimethylsilyl- and dimethylaminoethenyl-substituted cyclopentadienyl (Cp) rings present a nearly eclipsed conformation, and the two pairs of trimethylsilyl and dimethylaminoethenyl substituents on the Cp rings are arranged in an interlocked fashion.

From lithium bis(trimethylsilyl)amide with cyanoamine into triazine compounds: synthesis and structures of lithium 6-((trimethylsilyl)amido)-2,4-bis(dimethylamino)[1,3,5]triazines and their manganese and cobalt complexes.

Addition reactions of lithium bis(trimethylsilyl)amide with dimethylcyanamide lead to novel lithium salts of 6-((trimethylsilyl)amido)-2,4-bis(dimethylamino)[1,3,5]triazines [LLi(D)](2) (L = NC(NMe(2))NC(NMe(2))NC(NSiMe(3)); D = Me(2)NCN (1), Et(2)O (2)) and to the Mn and Co complexes [LL'M] (L' = N{N(SiMe(3))C(NMe(2))}(2); M = Mn (3), Co (4)); the structures of crystalline 1, 3, and 4 are reported. Their formation involves trimethylsilyl shifts, ring formation, and unusual Me(2)NSiMe(3) elimination.

Synthesis, crystal structure, magnetic property and thermal studies of [Ni(CH(3)COO)2·(NH2CH2Ph)4].

[Ni(CH(3)COO)(2)·(NH(2)CH(2)Ph)(4)] complex was synthesized using benzylamine and nickel acetate. The molecular structure of this complex was obtained by single crystal X-ray diffraction and characterized by elemental analysis, IR spectrometry and thermal analysis. The complex crystallized in the monoclinic space group P2(1)/n with cell parameters a=11.

A bulky silyl shift-directed synthesis of a silyl-linked amidinate-amidine and its Zr(IV) complex.

A novel silyl-linked amidinate-amidine monoanionic ligand 3 was synthesized by double additions of PhCN starting from silyl-linked bis(amino) monoanion 2, which underwent an intramolecular Li/H metathesis and double silyl shift. The related Zr(IV) complex 4 was prepared and confirmed by X-ray diffraction revealing a structural rearrangement from its precursor. The mechanisms for the reaction processes have been proposed.

Magnesium(II) complexes of 2,4-N,N'-disubstituted 1,3,5-triazapentadienyl ligands: synthesis and characterization of [N(Dipp)C(NMe2)NC(NMe(2))N(SiMe3)MgBr]2 and [N(R)C(R')NC(R')N(SiMe3)]2Mg (Dipp = 2,6-iPr2-C6H3, R = Ph, SiMe(3); R' = NMe2, 1-piperidino).

Treatment of the appropriate lithium or sodium 2,4-N,N'-disubstituted 1,3,5-triazapentadienate [RNC(R')NC(R')N(SiMe(3))M](2) (R = Ph, 2,6-(i)Pr(2)-C(6)H(3)(Dipp) or SiMe(3); R' = NMe(2) or 1-piperidino; M = Li or Na) with one or half equivalent portion of MgBr(2)(THF)(2) in Et(2)O under mild conditions furnishes in good yield the first structurally characterized molecular magnesium 2,4-N,N'-disubstituted 1,3,5-triazapentadienates [DippNC(NMe(2))NC(NMe(2))N(SiMe(3))MgBr](2) (1), [{RNC(R')NC(R')N(SiMe(3))}(2)Mg] (R = Ph, R' = NMe(2) 2; R = Ph, R' = 1-piperidino 3; R = SiMe(3), R' = 1-piperidino 4). The solid-state structure of 1 is dimeric and those of 2, 3, and 4 are monomeric. The ligand backbone NCNCN in 1 adopts a W-shaped configuration, while in 2, 3 and 4 adopts a U-shaped configuration.

Dichloridobis{6-methyl-2-[(trimethyl-silyl)amino]pyridine-κN}cobalt(II).

In the structure of the title compound, [CoCl(2)(C(9)H(16)N(2)Si)(2)], the Co(II) atom is located on an inversion center in a slightly distorted tetra-hedral environment formed by two chloride ions and the pyridine N atoms of two chelating 6-methyl-2-[(trimethyl-silyl)amino]pyridine ligands. The dihedral angle between the planes of the pyridine rings is 80.06 (5)°.

The ansa-bridged cyclo-penta-dienyl titanium complex [{η-C(5)Me(4)CH(2)-C(NMe(2))=N}TiCl(2)].

The title complex, dichlorido[N,N-di-methyl-2-(η(5)-tetra-methyl-cyclo-penta-dien-yl)acetamidinido-κN']titanium(IV), [Ti(C(13)H(20)N(2))Cl(2)], exhibits an unusual ansa-bridged conformation. The cyclo-penta-dienyl ring and the mean plane of the Ti-N=C-C-C fragment form a dihedral angle of 88.08 (11)°.

[μ-Bis(trimethyl-silyl)amido]bis-[μ-N,N-dimethyl-N',N''-bis-(trimethyl-silyl)guanidinato]-triangulo-tricopper(I).

The title compound, [Cu(3)(C(6)H(18)NSi(2))(C(9)H(24)N(3)Si(2))(2)], is a trinuclear Cu(I) complex. A crystallographic twofold axis passes through one Cu(I) atom and the N atom of the bis-(trimethyl-silyl)amide ligand that bridges between the other two Cu(I) atoms. The Cu-Cu bonds bridged by the guanadinate ligands [2.

2-Chloro-pyridine-3-carboxamide.

In the crystal structure of the title compound, C(6)H(5)ClN(2)O, the dihedral angle between the pyridine ring and the carboxamine group is 63.88 (8)°. Inter-molecular N-H⋯N and N-H⋯O hydrogen bonds link the mol-ecules into a two-dimensional network.

Synthesis and structures of selected triazapentadienate of Li, Mn, Fe, Co, Ni, Cu(I), and Cu(II) using 2,4-N,N'-disubstituted 1,3,5-triazapentadienate anions as ancillary ligands: [N(Ar)C(NMe2)NC(NMe2)N(R)](-) (Ar = Ph, 2,6-(i)Pr2-C6H3; R = H, SiMe3).

Addition reaction of ArN(SiMe 3)M (Ar = Ph or 2,6 - (i) Pr 2-C 6H 3 (Dipp); M = Li or Na) to 2 equivalents of alpha-hydrogen-free nitrile RCN (R = dimethylamido) gave the dimeric [M{N(Ar)C(NMe 2)NC(NMe 2)N(SiMe 3)}] 2 ( 1a, Ar = Ph, M = Li; 1b, Ar = Ph, M = Na; 1c, Ar = Dipp, M = Li). 1d was obtained by hydrolysis of 1c at ambient temperature. Treatment of a double ratio of 1a or 1b with anhydrous MCl 2 (M = Mn, Fe, Co) yielded the 1,3,5-triazapentadienato complexes [M{N(Ph)C(NMe 2)NC(NMe 2)N(SiMe 3)} 2] (M = Mn, 2; Fe, 3; Co, 4) and with NiCl 2.

Syntheses of 2,4-disubstituted 1,3,5-triazapentadienyl ligands having two guanidinato moieties and their use in the isolation of copper(I) complexes.

2,4-N,N'-Disubstituted 1,3,5-triazapentadienyl ligands as their lithium salts [Li{(N(R)C(R'))2N}]2 [where R = SiMe3 here and hereafter and R' = dimethylamino (1) or 1-piperidino (2)] were synthesized via the reactions of LiN(SiMe3)2 with 2 equiv of the alpha-hydrogen-free carbonitrile dimethylcyanamide or 1-piperdinecarbonitrile and used in the isolation of the two-coordinate copper(I) complexes [Cu{(N(R)C(R'))2N}]2 [R' = dimethylamino (3) and 1-piperidino (4)]. Complex 2 features a twisted W-shaped ligand backbone in the solid state. Complexes 3 and 4 show an unusual 12-membered ring dinuclear copper( I) triazapentadienyl and a less expressed ability to form a stable delocalized triazapentadienyl system.

N-o-Tolyl-benzamidine.

The asymmetric unit of the title compound, C(14)H(14)N(2), contains two independent mol-ecules with slightly different conformations; the dihedral angles formed by aromatic rings in the two mol-ecules are 73.2 (1) and 75.0 (1)°.

Preparation and characterization of inclusion complexes of pefloxacin mesylate with three kinds of cyclodextrins.

The ability of alpha-cyclodextrin, beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin (alpha-CD, beta-CD and HP-beta-CD) to break pefloxacin mesylate (PM) aggregates by forming inclusion complexes has been studied using 1H NMR (nuclear magnetic resonance spectroscopy), 13C NMR and fluorescence spectra. The inclusion constants are determined to compare the corresponding inclusion capacity. Solid-inclusion complexes of PM with CDs are synthesized by coprecipitation method, and all the inclusion ratios are found to be 1:1.