Synthesis of Hexadentate Hexahydro-1,3,5-triazine-Based Ligands and their Copper(I) Complexes

Summary.  Hexadentate ligands were formed by the reaction of primary dimethylaminoethyl- or methoxyethylamines with formaldehyde. The resulting N, N′, N″-functionalized hexahydro-1,3,5-triazines contain pending amino or ether functionalities which are able to coordinate to metals in addition to the ring nitrogen atoms. Both ligands were reacted with CuBr, and novel tricopper clusters were isolated and characterized by X-ray structure analysis. In these compounds a ring nitrogen atom, the pending amino or ether functionality, and two bridging bromine atoms coordinate each of the copper atoms. Received January 22, 2002; accepted (revised) March 22, 2002     

Synthesis and Characterization of Bridged Bimetallic Complexes. I. Copper(II) Complexes with Conjugated Diimine Ligands

A series of binucleating Uganda with fully conjugated π-systems have been synthesized. Homobinuclear copper(II) complexes of the form [(Cu(dien)ClO₄)₂L]-(ClO₄)₂, where dien is diethylenetriamine and L is binucleating ligand, were prepared. Mononuclear complexes, with structure similar to that of the preceeding compounds, [Cu(dien)L′(ClO₄)](ClO₄) were synthesized as reference compounds. The infrared spectra, elctronic spectra and magnetic properties were studied. The inductive effect, steric effect and the effect of the length of the conjugated π-system on the magnetic exchange interaction between the two copper ions are discussed. The electrochemical properties of these complexes were investigated by cyclic voltammetry. The copper ions showed the cooperative phenomena and a quasi-reversible sequential transfer of two electrons at the same potential.     

First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

Three new complexes with phosphanylphosphido ligands, [Cu₄{μ₂‐P(SiMe₃)‐PtBu}₄] ( 1 ), [Ag₄{μ₂‐P(SiMe₃)‐PtBu₂}₄] ( 2 ) and [Cu{η¹‐P(SiMe₃)‐PiPr₂}₂]^–[Li(Diglyme)₂]⁺ ( 3 ) were synthesized and structurally characterized by X‐ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane tBu₂P‐P(SiMe₃)Li · 2.7THF with CuCl and [iBu₃PAgCl]₄, respectively. The X‐ray diffraction analysis revealed that the complexes 1 and 2 present macrocyclic, tetrameric form with Cu₄P₄ and Ag₄P₄ core. Complex 3 was prepared in the reaction of CuCl with a different derivative of lithiated diphosphane iPr₂P‐P(SiMe₃)Li · 2(Diglyme). Surprisingly, the X‐ray analysis of 3 revealed that in this reaction instead of the tetramer the monomeric form, ionic complex [Cu{η¹‐P(SiMe₃)‐PiPr₂}₂]^–[Li(Diglyme)₂]⁺ was formed.     

含双二苯基膦甲烷双核铜(I)配合物的合成及性质

利用配体取代反应合成了四种含双二苯基膦甲烷(dppm)的双铜(Ⅰ)配合物[Cu2(dppm)2L2](NO3)2(配体L分别是2,2'-联吡啶(1)、邻菲咯啉(2)、2,9-二甲基-邻菲咯啉(3)、吡啶(4)],并经核磁、热分析、光电子能谱等方法表征了配合物的性质.配合物(1)的晶体结构显示,dppm作为桥式双齿配体、联吡啶作为双齿配体分别与铜原子形成四面体配位结构,硝酸根离子位于配合物外界.     

New Copper(II) Complexes Containing 2-Furoic Hydrazide and 5-Nitro-2-Furoic Hydrazide Ligands: Synthesis,Thermal, Magnetic and Spectroscopic Characterization

Two new copper(II) complexes, [Cu₂(L¹)₄(H₂O)₂](SO₄)₄· 2H₂O and [Cu(L²)₂(H₂O)₂]SO₄, were isolated containing 2-furoic hydrazide and 5-nitro-2-furoic hydrazide ligands, respectively. The complexes were characterized by thermal, magnetic and spectroscopic techniques, showing a distorted tetragonal environment around the metal ion. Compound (1), containing 2-furoic hydrazide as the ligand, appears to be dimeric in the solid state, with substituted hydrazine acting as a bidentate bridging ligand. On the contrary, a monomeric species was observed with the 5-nitro-2-furoic hydrazide ligand, probably in the cis configuration, for compound (2). Magnetic measurements for the binuclear copper(II) complex (1) were carried out at low temperatures, in the 2–300 K range, and a magnetic field of 500 G, indicating that besides an intramolecular ferromagnetic interaction between the two Cu(II) centers, for which J/k = 1.07 K, further weak antiferromagnetic interactions between adjacent dimers, with Jz/k =–0.95 K, should be taken into account. However, in MeOH/H₂O solution, evidence of equilibria involving the dimer (1) and the corresponding mononuclear cis and trans species was obtained from e.p.r. spectra.     

Copper(I) Complexes of Anionic Tridentate CNC Pincer Ligands

New monoanionic CNC pincer ligands, [N{SiMe₂CH₂(RIm)}₂]^– (R = tBu, iPr, Ph) featuring three different N-heterocyclic carbenes and a disilylamido moiety is reported. Treatment of the lithium salt of [N{SiMe₂CH₂(RIm)}₂]^– with Cu^IOTf afforded the corresponding copper complexes [N{SiMe₂CH₂(RIm)}₂]Cu in 41–56 % yield. X-ray crystal structures of [N{SiMe₂CH₂(RIm)}₂]Cu show that they are monomeric and feature three-coordinate, pseudo T-shaped copper(I) sites. The X-ray crystal structure of one of the precursor lithium complexes, [N{SiMe₂CH₂(tBuIm)}₂]Li is also presented.     

Synthesis and Physico-Chemical Properties of Homoleptic Copper(I) Complexes with Asymmetric Ligands as a DSSC Dye

To develop low-cost and efficient dye-sensitized solar cells (DSSCs), we designed and prepared three homoleptic Cu(I) complexes with asymmetric ligands, M1, M2, and Y3, which have the advantages of heteroleptic-type complexes and compensate for their synthetic challenges. The three copper(I) complexes were characterized by elemental analysis, UV-vis absorption spectroscopy, and electrochemical measurements. Their absorption spectra and orbital energies were evaluated and are discussed in the context of TD-DFT calculations. The complexes have high V_OC values (0.48, 0.60, and 0.66 V for M1, M2, and Y3, respectively) which are similar to previously reported copper(I) dyes with symmetric ligands, although their energy conversion efficiencies are relatively low (0.17, 0.64, and 2.66%, respectively).     

Novel Copper(I) Complexes and Clusters with Phosphorus-Sulfur and Sulfur-Sulfur Containing Ligands

Abstract

The synthesis and coordination chemistry of ligands bearing PS donor groups in complexes with copper(I) halides, in particular thiophosphites, thiophosphonites, and thiophosphinites, are described.     

Synthesis and Coordination of Tripodal-Containing Copper(I) Complexes

Reaction of copper(I) chloride with 2,2-bis(diphenylphosphinomethyl)-l-phenylthiopropane P₂S produced a dimeric species [(P₂S)CuC1]₂ (2). Treatment of 2 with silver nitrate in acetonitrile gave a hexameric crystalline metal complex {[(P₂S)Cu(CH₃CN)]₆⁺6NO₃} (4), which had a “cyclodextrin-type” structure. A linear polymeric copper complex [(P₂S)Cu(NO₃)]_n was obtained by recrystallization of 4 in chloroform. These complexes were characterized by single crystal analyses, and their coordination behaviors in solution are discussed.     

无机化学综合实验:Cu(I)配合物的合成与光致发光性能

Cu（I）配合物的合成与光致发光性能实验是结合无机化学中的配合物基础知识和前沿研究热点设计的综合性实验,包括配合物的制备和光致发光性质表征。本实验中分别制备了立方烷、阶梯状、二聚体等不同结构和不同配体的Cu（I）配合物,深入研究了光致发光性能与配合物结构之间的关系。该实验共需12学时完成,实验过程包括配合物制备、减压过滤、荧光光谱测试与分析等,涉及沉淀溶解、配位等多种反应类型和分子光物理性质探究。该综合性实验对实验设备要求低,实验现象明显,产率高,教学过程可操作性强,综合性强。教学实践表明,该实验能显著激发学生学习兴趣,不仅可以让学生加深对无机化学基础知识的理解,还可以获取前沿知识,对提高学生的综合实验能力,培养创新型、复合型人才具有重要意义。     

Synthesis and Properties of Copper Trimesinate Complexes with Polypyridine Ligands

Russian Journal of General Chemistry - Copper trimesinate complexes Cu3(BTC)2L3 and Cu3(BTC)2L with polypyridine ligands, such as 2,2′-bipyridyl, 1,10-phenanthroline, and...     

Metal Complexes Derived from Hydrazoneoxime Ligands: I. Synthesis,Characterization and Magnetochemical Studies of (Acylhydrazoneoxime) Copper(II) Complexes

Reactions of 2-hydroxyimino-1-methylpropylidene (acetyl-) and (benzoylhydrazine) with copper(II) chloride, nitrate and acetate were studied. Three types of copper(II) complexes of general formula [Cu(H₂L)Cl₂], [{Cu(HL)}₂][sdot]2NO₃[sdot]nH₂O and [{Cu(L)}₂], where H₂L, HL, and L refer, respectively, to the neutral, monoanionic and dianionic ONN tridentate acylhydrazoneoxime ligands, were isolated and characterized. Variable-temperature magnetic susceptibility measurements for [Cu(H₂L)Cl₂] suggest Curie-Weiss behavior. Both [{Cu(HL)}₂][sdot]2NO₃[sdot]nH₂O and [{Cu(L)}₂] show strong antiferromagnetic exchange coupling with ? 2J values of 898-934 and 718-757 cm^?1, respectively, indication dimeric structures with oximate bridges.     

Non-Symmetrical Sterically Challenged Phenanthroline Ligands and Their Homoleptic Copper(I) Complexes with Improved Excited-State Properties

A strategy is presented to improve the excited state reactivity of homoleptic copper–bis(diimine) complexes CuL₂⁺ by increasing the steric bulk around Cu^I whereas preserving their stability. Substituting the phenanthroline at the 2-position by a phenyl group allows the implementation of stabilizing intramolecular π stacking within the copper complex, whereas tethering a branched alkyl chain at the 9-position provides enough steric bulk to rise the excited state energy E⁰⁰. Two novel complexes are studied and compared to symmetrical models. The impact of breaking the symmetry of phenanthroline ligands on the photophysical properties of the complexes is analyzed and rationalized thanks to a combined theoretical and experimental study. The importance of fine-tuning the steric bulk of the N–N chelate in order to stabilize the coordination sphere is demonstrated. Importantly, the excited state reactivity of the newly developed complexes is improved as demonstrated in the frame of a reductive quenching step, evidencing the relevance of our strategy.     

Synthesis and Characterization of Tris(oxazolinyl)borato Copper(II) and Copper(I) Complexes

The reaction of To^MTl (To^M=tris(4,4-dimethyl-2-oxazolinyl)phenylborate) and CuBr₂ in benzene at 60 °C provides To^MCuBr ( 1 ) as an entry-point into tris(oxazolinyl)phenylborato copper chemistry. To^MCuO^tBu ( 2 ) and To^MCuOAc ( 3 ) are prepared by the reactions of To^MCuBr with KO^tBu and NaOAc, respectively. To^MCuO^tBu is transformed into (To^MCuOH)₂ ( 4 ) through hydrolysis. NMR, FT-IR, and EPR spectroscopies are used to determine the electronic and structural properties of these copper(II) compounds, and the solid-state structures were characterized by X-ray crystallography. Reduction of copper is observed upon treatment of To^MCuO^tBu with phenylsilane in an attempt to synthesize monomeric copper(II) hydride. To^MCu ( 5 ) and To^M₂Cu ( 6 ) were independently synthesized and characterized for comparison.     

Structural and Electrochemical Comparison of Copper(II) Complexes with Tripodal Ligands

A series of copper(II) complexes with tripodal polypyridylmethylamine ligands, such as tris(2-pyridylmethyl)amine (tpa), ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine (Me(1)tpa), bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine (Me(2)tpa), and tris((6-methyl-2-pyridyl)methyl)amine (Me(3)tpa), have been synthesized and characterized by X-ray crystallography. [Cu(H(2)O)(tpa)](ClO(4))(2) (1) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.029(7) ?, b = 9.268(2) ?, c = 17.948(5) ?, beta = 113.80(3) degrees, and Z = 4 (R = 0.061, R(w) = 0.059). [CuCl(Me(1)tpa)]ClO(4) (2) crystallized in the triclinic system, space group P&onemacr;, with a = 13.617(4) ?, b = 14.532(4) ?, c = 12.357(4) ?, alpha = 106.01(3) degrees, beta = 111.96(2) degrees, gamma = 71.61(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.037). [CuCl(Me(2)tpa)]ClO(4) (3) crystallized in the monoclinic system, space group P2(1)/n, with a = 19.650(4) ?, b = 13.528(4) ?, c = 8.55(1) ?, beta = 101.51(5) degrees, and Z = 4 (R = 0.071, R(w) = 0.050). [CuCl(Me(3)tpa)][CuCl(2)(Me(3)tpa)]ClO(4) (4) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.698(6) ?, b = 14.687(7) ?, c = 19.475(4) ?, beta = 97.13(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.038). All the Cu atoms of 1-4 have pentacoordinate geometries with three pyridyl and one tertiary amino nitrogen atoms, and a chloride or aqua oxygen atom. Nitrite ion coordinated to the Cu(II) center of Me(1)tpa, Me(2)tpa, and Me(3)tpa complexes with only oxygen atom to form nitrito adducts. The cyclic voltammograms of [Cu(H(2)O)(Me(n)()tpa)](2+) (n = 0, 1, 2, and 3) in the presence of NO(2)(-) in H(2)O (pH 7.0) revealed that the catalytic activity for the reduction of NO(2)(-) increases in the order Me(3)tpa < Me(2)tpa < Me(1)tpa < tpa complexes.     

Gold(I) and Silver(I) Complexes with Thioether Functionalized Silylamido Ligands

The thioether functionalized aminosilanes Me₂Si(NH‐C₆H₄‐2‐SR)₂ (R = Ph, Me) were lithiated with nBuLi and subsequently reacted with AgCl in the presence of PMe₃ or with [AuCl(PMe₃)]. In the case of Me₂Si(NH‐C₆H₄‐2‐SPh)₂ the dinuclear complexes [M₂{Me₂Si(NC₆H₄‐2‐SPh)₂}(PMe₃)₂] (M = Ag; Au) were isolated. The analogous reactions starting from Me₂Si(NH‐C₆H₄‐SMe)₂ afforded the dinuclear gold complex [Au₂{Me₂Si(NC₆H₄‐2‐SMe)₂}(PMe₃)₂] and the tetranuclear silver complex [Ag₄{Me₂Si(NC₆H₄‐2‐SMe)₂}₂(PMe₃)₂]. In the dinuclear compounds of the type [M₂{Me₂Si(NC₆H₄‐2‐SR)₂}(PMe₃)₂], each of the silylamide N atoms is connected to a M(PMe₃) group to give a nearly linear N–M–P arrangement with Ag–N and Au–N bonds in the range of 212.0(4)–213.3(4) pm and 205.3(3)–208.1(9) pm, respectively. [Ag₄{Me₂Si(NC₆H₄‐2‐SMe)₂}₂(PMe₃)₂] consists of a central Si₂N₄Ag₂ ring with linearly coordinated Ag atoms (Ag‐N: 223.1(4)–222.1(4) pm) and two peripheral Ag(PMe₃) units, which are connected to the amido N atoms in a chelating mode. The relatively short transannular Ag ··· Ag separation (277.6(1) pm) within the Si₂N₄Ag₂ ring hints for argentophilic interactions. The peripheral Ag atoms are three coordinated with Ag–N distances of 233.9(4)–242.8(4) pm.     

两种三齿多吡啶铜(Ⅱ)配合物的合成、表征及其与DNA的作用

本文合成了2个三齿多吡啶铜(Ⅱ)配合物[Cu(phpi)Cl₂]·H₂O和[Cu(tpy)Cl₂]·2H₂O(phpi=2-(苯并咪唑基-2)-1，10-邻菲咯啉，tpy=2，2:6′，2″-三联吡啶)，并通过元素分析、摩尔电导率、红外光谱、紫外光谱对其进行了表征。应用电子吸收光谱、荧光光谱和粘度法研究了配合物与DNA的相互作用。在抗坏血酸存在下，利用琼脂糖凝胶电泳方法研究了配合物对pBR322 DNA的切割作用并对其作用机理作了初步探讨。     

Synthesis and Crystal Structures of Novel Copper(I) Clusters with Bridging Silyl Amide Ligands

Treatment of copper(I) chloride with R₂Si(NLiPh)₂ (R = Me, Ph) in thf led to the formation of the octanuclear cluster compounds [Cu₈{(R₂Si(NPh)₂}₄] [R = Me ( 1 ), Ph ( 2 ).] Compound 1 crystallizes in the tetragonal space group P4/n, with a = 1505.41(5) and c = 1911.32(7) pm. The X‐ray crystal structure determination revealed a cube shaped Cu₈ cluster core with μ₄ bridging Me₂Si(NPh)₂^2– ligands. The copper atoms display an almost linear coordination with Cu–N distances in the range of 191.1(3)–191.4(3) pm. The Cu–Cu distances are 265.7(1)–267.3(1) pm. Compound 2 forms monoclinic crystals, space group P2₁/n, with a = 1461.87(4), b = 2483.77(6), c = 2725.49(8) pm, β = 100.77(1)°. The cluster core of compound 2 consists formally of two mutually perpendicular arranged trigonal prisms, which share a common square face. Like in the case of compound 1 the square faces of the cluster core are capped by μ₄ bridging Ph₂Si(NPh)₂^2– ligands. The copper atoms adopt a nearly linear N–Cu–N coordination with Cu–N distances of 190.0(4)–195.1(4) pm. The Cu–Cu distances are 252.3(1)–305.6(1) pm.