Copper(I) cyanide networks: synthesis, luminescence behavior and thermal analysis. Part 1. Diimine ligands

Metal-organic networks of CuCN with diimines (L) = pyrazine (Pyz), 2-aminopyrazine (PyzNH(2)), quinoxaline (Qox), phenazine (Phz), 4,4'-bipyridyl (Bpy), pyrimidine (Pym), 2-aminopyrimidine (PymNH(2)), 2,4-diaminopyrimidine (Pym(NH(2))(2)), 2,4,6-triaminopyrimidine (Pym(NH(2))(3)), quinazoline (Qnz), pyridazine (Pdz), and phthalazine (Ptz) were studied. Open reflux reactions produced complexes (CuCN)(2)(L) for L = Qox, Phz, Bpy, PymNH(2), Pym(NH(2))(2), Qnz, and Pdz and (CuCN)(3)(L) complexes for L = Pyz, PyzNH(2), Qox, Bpy, Pym(NH(2))(3), and Pdz. Also produced were (CuCN)(3)(Pyz)(2), (CuCN)(PyzNH(2)), (CuCN)7(Pym)(2), (CuCN)(5)(Qnz)(2) and (CuCN)(5)(Ptz)(2). X-ray structures are presented for (CuCN)(2)(Pdz), (CuCN)(2)(PymNH(2)), and (CuCN)(7)(Pym)(2). Hydrothermal reactions yielded additional X-ray structures of (CuCN)(2)(PyzNH(2)), (CuCN)(3)(Pym(NH(2))(2)), (CuCN)(4)(Qnz), a second (CuCN)(2)(Pdz) phase, (CuCN)(5)(Pdz)2, (CuCN)(2)(Ptz), and (CuCN)(7)(Ptz)2. Structural trends, including cuprophilic interactions and cyano-bridged Cu(2)(CN)(2) dimer formation, are discussed. Particularly short Cu...Cu interactions are noted for the novel 4- and 5-coordinate Cu(2)(CN)(2) dimers. Thermal analyses show that most of the complexes decompose with loss of L around 160-180 degrees C. Luminescence behavior is relatively weak in the products.     

Synthesis and characterization of copper(I) halide/pseudohalide adducts of 2-benzoylpyridine and x-ray crystal structure of [di-μ-iodo-bis(N,O-2-benzoylpyridine)dicopper(I)]

Dark-brown copper(I) complexes of the type CuXL, for X = Cl, Br, I, SCN and N₃, and orange-yellow complexes of the type (CuX)₂L, for X = Cl or Br, where L = 2-benzoylpyridine, have been prepared and characterized. All complexes exhibit strong CT bands in the visible region and gave non-conducting solutions in acetone and nitrobenzene. The IR spectral data suggest that 2-benzoylpyridine acts as a monodentate ligand in the orange-yellow complexes and as a bidentate chelating ligand in the brown complexes, whereas bridging halides and pseudohalides exist in both types. The structure of the 1 : 1 black iodide complex, as determined by X-ray crystallography, features a discrete, centrosymmetric [CuI(2-benzoylpyridine)]₂ molecule with a short CuCu distance of 2.587(1) Å. Each copper atom in the dimeric molecule is tetrahedrally coordinated by two μ-iodine atoms and the carbonyl oxygen and nitrogen atoms of the chelating 2-benzoylpyridine ligand. The orange-yellow complexes display visible emission when excited in the UV region, whereas the brown complexes do not.     

Zur Reaktion der Alkin‐Kupfer(I)‐Komplexe [CuX(S‐Alkin)] (X = Cl,Br, I; S‐Alkin = 3,3,6,6‐Tetramethyl‐1‐thia‐4‐cycloheptin) mit den Phosphanen PMe3 und Ph2PCH2CH2PPh2 (dppe)

Organometallic Compounds of Copper. XVIII. On the Reaction of the Alkyne Copper(I) Complexes [CuX(S‐Alkyne)] (X = Cl, Br, I; S‐Alkyne = 3,3,6,6‐Tetramethyl‐1‐thiacyclohept‐4‐yne) with the Phosphanes PMe₃ and Ph₂PCH₂CH₂PPh₂ (dppe) The alkyne copper(I) halide complexes [CuX(S‐Alkyne)]_n ( 2 ) ( 2 a : X = Cl, 2 b : X = Br, 2 c : X = I; S‐Alkyne = 3,3,6,6‐tetramethyl‐1‐thiacyclohept‐4‐yne; n = 2, ∞) add the phosphanes PMe₃ and Ph₂PCH₂CH₂PPh₂ (dppe) to form the mono‐ and dinuclear copper compounds [(S‐Alkyne)CuX(PMe₃)] ( 6 ) ( 6 a : X = Cl, 6 b : X = Br) and [(S‐Alkyne)CuX(μ‐dppe)CuX(S‐Alkyne)] ( 7 a : X = Cl, 7 b : X = Br, 7 c : X = I), respectively. By‐product in the reaction of 2 a with dppe is the tetranuclear complex [(S‐Alkyne)Cu(μ‐X)₂Cu(μ‐dppe)₂Cu(μ‐X)₂Cu(S‐Alkyne)] ( 8 ). In case of the compounds 7 prolonged reaction times yield the alkyne‐free dinuclear copper complexes [Cu₂X₂(dppe)₃] ( 9 ) ( 9 a : X = Cl, 9 b : X = Br, 9 c : X = I)). X‐ray diffraction studies were carried out with the new compounds 6 a , 6 b , 7 b , 8 , and 9 c .     

T-shaped platinum boryl complexes: synthesis and structure

A series of cationic T-shaped 14-electron boryl complexes of the type trans-[(Cy(3)P)(2)Pt{B(X)X'}](+) (X=Br; X'=ortho-tolyl, tBu, NMe(2), piperidyl, Br; XX'=(NMe(2))(2), catecholato) were synthesized by halide abstraction from trans-[(Cy(3)P)(2)Pt(Br){B(X)X'}] (Cy=cyclohexyl) with Na[BAr(f) (4)] (Ar(f)=3,5-(CF(3))(2)C(6)H(3)), K[B(C(6)F(5))(4)], or Na[BPh(4)]. X-ray diffraction studies were performed on all compounds, revealing a subtle correlation between the trans-influence of the boryl moiety and the Pt--H and Pt--C separations. However, no notable agostic C--H interaction with the platinum center was detected. trans-[(Cy(3)P)(2)Pt(BCat)](+) (Cat=catecholato), the complex with the shortest Pt--H and Pt--C distances, was treated with Lewis bases (L), forming compounds of the type trans-[(Cy(3)P)(2)Pt(L)(BCat)](+), thus proving a decisive influence of the degree of trans-influence exerted by the boryl ligands on the chemical reactivity of the title complexes. Another point that was investigated and clarified is the different behavior of trans-[(Cy(3)P)(2)Pt(Br){B(Br)Mes}] (Mes=mesityl) towards K[B(C(6)F(5))(4)] with formation of the borylene species trans-[(Cy(3)P)(2)Pt(Br)(BMes)](+).     

Trinuclear-based copper(I) pyrazolate polymers: effect of trimer π-acid···halide/pseudohalide interactions on the supramolecular structure and phosphorescence

Under different situations, solvothermal reactions of 3,5-diethyl-4-(4-pyridyl)-pyrazole (HL) with CuX or CuX(2) (X = Cl, Br, I, and SCN) afforded five copper(I) coordination polymers, {CuX[CuL](3)·solvent}(n) (X = Cl, 1; Br, 2; I, 3; X = SCN and solvent = MeCN, 4) and {Cu(2)I(2)[CuL](3)}(n) (5). X-ray diffraction analyses show that all the complexes have trinuclear [CuL](3) (referred as Cu(3)) secondary building units featuring planar nine-membered Cu(3)N(6) metallocycles with three peripheral pyridyl groups as connectors, which are further linked by CuX or Cu(2)X(2) motifs to generate single- or double-strand chains. Interestingly, the Cu(I) atoms within the Cu(3) units in 1-5 behave as coordinatively unsaturated π-acid centers to contact soft halide/pseudohalide X atoms of CuX and Cu(2)X(2) motifs, which lead to novel sandwich substructures of [(Cu(3))(Cu(2)X(2))(Cu(3))] (X = Br, I, and SCN) in 2-4. In addition, both the π-acid [Cu(3)]···X contacts and intertrimer Cu···Cu interactions contribute to the one-dimensional (1D) double-strand and 2D/3D supramolecular structures of 1-5. All of these complexes exhibit high thermostability and bright solid-state phosphorescence upon exposure to UV radiation at room temperature. The emissions arise from the mixtures of metal-centered charge transfer, metal to ligand charge transfer, and halide-to-ligand charge transfer excited states, and can be tuned by intermolecular π-acid [Cu(3)]···halide/pseudohalide contacts.     

Copper(I) coordination polymers [{Cu(mu-X)}2{RP(mu-NtBu)}2]n (R = OC6H4OMe-o; X = Cl, Br, and I) and their reversible conversion into mononuclear complexes [CuX{(RP(mu-NtBu)2}2]: synthesis and structural characterization

The reactions of cyclodiphosphazane cis-[tBuNP(OC6H4OMe-o)]2 (1) with 2 equiv of CuX in acetonitrile afforded one-dimensional Cu(I) coordination polymers [Cu2X2{tBuNP(OC6H4OMe-o)}2]n (2, X = Cl; 3, X = Br; 4, X = I). The crystal structures of 2 and 4 reveal a zigzag arrangement of [P(mu-N)(2)P] and [Cu(mu-X)(2)Cu] units in an alternating manner to form one-dimensional Cu(I) coordination polymers. The reaction between 1 and CuX in a 2:1 ratio afforded mononuclear tricoordinated copper(I) complexes of the type [CuX{(tBuNP(OC6H4OMe-o))2}2] (5, X = Cl; 6, X = Br; 7, X = I). The single-crystal structures were established for the mononuclear copper(I) complexes 5 and 6. When the reactant ratios are 1:1, the formation of a mixture of polymeric and mononuclear products was observed. The Cu(I) polymers (2-4) were converted into the mononuclear complexes (5-7) by reacting with 3 equiv of 1 in dimethyl sulfoxide. Similarly, the mononuclear complexes (5-7) were converted into the corresponding polymeric complexes (2-4) by reacting with 3 equiv of copper(I) halide under mild reaction conditions.     

Synthesis and characterization of rhenium-copper sulfide cluster complexes [(Ph3P)2N][Re3(CuX)(mu3-S)4Cl6(PMe2Ph)3] (X = Cl, Br, I)

The reaction of a trinuclear rhenium sulfide cluster compound Re3S7Cl7 with dimethylphenylphosphine and CuX2 (X = Cl or Br) or CuX (X = Cl, Br, or I) formed tetranuclear cluster complexes [(Ph3P)2N][Re3(CuX)(mu3-S)4Cl6(PMe2Ph)3] (X = Cl, Br, or I). Their solutions have the characteristic intense blue color with visible spectral bands near 600 nm. Single-crystal X-ray structures show that three mu-S atoms in the intermediate trinuclear rhenium complex coordinate to a copper atom, forming elongated tetrahedral structures in which Re-Cu bonding interaction is negligible (Re-Cu distances are 3.50 to approximately 3.54 A as compared with Re-Re distances ranging from 2.69 to 2.81 A).     

Tri- and tetracoordinate copper(I) complexes bearing bidentate soft/hard SN and SeN ligands based on 2-aminopyridine

The coordination properties of the EN ligands N-(2-pyridinyl)amino-diphenylphosphine sulfide, N-(2-pyridinyl)amino-diisopropylphosphine sulfide, N-(2-pyridinyl)amino-diphenylphosphine selenide, N-(2-pyridinyl)amino-diisopropylphosphine selenide towards copper(I) precursors CuX (X = Br, I), [Cu(IPr)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), and [Cu(CH(3)CN)(4)]PF(6) were studied. Treatment of CuX with EN ligands resulted in the formation of tricoordinate complexes of the type [Cu(κ(2)(E,N)-EN)X]. The reaction of [Cu(IPr)Cl] with EN ligands, followed by halide abstraction with AgSbF(6), afforded cationic tricoordinate complexes [Cu(κ(2)(S,N)-EN)(IPr)](+), while the reaction of [Cu(CH(3)CN)(4)](+) with two equivalents of EN ligands yielded tetrahedral complexes [Cu(κ(2)(E,N)-EN)(2)](+). Halide removal from [Cu(κ(2)(S,N)-SN)I] with silver salts in the presence of L = CH(3)CN and CNtBu afforded dinuclear complexes of the type [Cu(κ(2)(S,N),μ(S)-SN)(L)](2)(2+) containing bridging SN ligands. With the terminal alkynes HC≡CC(6)H(4)Me and HC≡CC(6)H(4)OMe, complexes of the formula [Cu(κ(2)(S,N)-SN-iPr)(η(2)-HC≡CC(6)H(4)Me)](+) and [Cu(κ(2)(S,N)-SN-iPr)(η(2)-HC≡CC(6)H(4)OMe)](+) were obtained. The mononuclear nature of these compounds was supported by DFT calculations. Most complexes were also characterized by X-ray crystallography.     

Diboryl and Diboranyl Porphyrin Complexes: Synthesis,Structural Motifs,and Redox Chemistry: Diborenyl Porphyrin or Diboranyl Isophlorin?

The syntheses of diboryl porphyrin complexes [(BX2)2(ttp)] (ttp: dianion of tetra-p-tolylporphyrin) and the B-B single-bond diboranyl complexes [(BX)2(ttp)] (X=F, Cl, Br, I) are given. The former are prepared from the reactions of BX3 (X=F, Cl) with [Li2(ttp)] and the latter from B(2)Cl(4) (X=Cl), the reaction of SbF3 with [(BCl)2(ttp)] (for X=F), and, in the cases of X=Br or I, in a remarkable reductive coupling reaction resulting directly from the reaction of BBr3 or BI3 with [Li2(ttp)]. Density functional theory (DFT) calculations on the thermochemical parameters for the reductive coupling reactions (and those calculated for related dipyrromethene complexes) indicate that a combination of the reducing ability of bromide and iodide ions combined with the constrained environment of the porphyrin ligand contribute to the driving force. The reductive coupling is also observed in the reaction of [(BCl2)2(ttp)] with nBuLi to give [(BnBu)2(ttp)], which was characterised crystallographically. The reaction of [(BCl)2(ttp)] with catechol gives a boron catecholato porphyrin complex, [B2(O(2)C(6)H(4))(ttp)]. Chloride abstraction from [(BCl)2(ttp)] gives the planar dication [B2(ttp)]2+, whereas chemical reduction of [(BCl)2(ttp)] by using magnesium anthracenide gives a neutral complex, [B(2)(ttp)], in which the TTP ligand has been reduced by two electrons to give an unusual example of an isophlorin complex. The cationic and neutral complexes [B2(ttp)]2+ and [B2(ttp)] were characterised through a combination of spectroscopic data that is supported by DFT calculations on the porphine analogues.     

Mechanochemical synthesis in copper(II) halide/pyridine systems: single crystal X-ray diffraction and IR spectroscopic studies

Whereas complexes of divalent metal halides (X = Cl, Br, I) with/from pyridine commonly crystallise as trans-[M(py)(4)X(2)]·2py, M on a site of 222 symmetry in space group Ccca, true for CuCl(2) and CuBr(2) in particular, the copper(II) iodide adduct is of the form [Cu(py)(4)I]I·2py, Cu on a site of mm2 symmetry in space group Cmcm, and five-coordinate (square-pyramidal), the same cationic species also being found in 2[Cu(py)(4)I](I(3))·[(py)(2)Cu(μ-I)(2)Cu(py)(2)] (structurally defined). Bromide or N-thiocyanate may be substituted for the unbound iodide ion in the solvated salt, resulting in complexes which crystallize in space group Ccca, but with both anions and the metal atom disordered. In [Cu(py)(4)(I(3))(2)], a pair of long Cu···I contacts approach a square-planar Cu(py)(4) array. Assignments of the ν(CuN) and ν(CuX) (X = Br, I, SCN) bands in the far-IR spectra are made, the latter with the aid of analogous assignments for [Cu(py)(2)X(2)] (X = Cl, Br), which show a dependence of ν(CuX) on the Cu-X bond length that is very similar to that determined previously for copper(i) halide complexes. The structure of the adventitious complex [(trans-)(H(2)O)(py)(4)CuClCu(py)(4)](I(3))(3)·H(2)O is also recorded, with six- and five-coordinate copper atoms; rational synthesis provides [{Cu(py)(4)}(2)(μ-Cl)](I(3))(3)·H(2)O with one water molecule less. In [{Cu(py)(4)Cl}((∞|∞))](I(3))·3py, square pyramidal [Cu(py)(4)Cl](+) cations, assisted by Cl···Cu interactions, stack to give rise to infinite polymeric strings. Several of these compounds were prepared mechanochemically, illustrating the applicability of this method to syntheses involving redox reactions as well as to complex syntheses involving up to five components. The totality of results demonstrates that the [Cu(II)(py)(4)] entity can be stabilized in an unexpectedly diverse range of mononuclear and multinuclear complexes through the presence of lattice pyridine molecules, the bulky triiodide ion, or a combination of both.     

From a trinuclear platinum(III) phosphido derivative to a platinum(II) cluster: formation of a P-C bond

Reaction of the trinuclear Pt(III)-Pt(III)-Pt(II) [(C6F5)2Pt(III)(mu-PPh2)2Pt(III)(mu-PPh2)2Pt(C6F5)2] (2) derivative with NBu4Br or NBu4I results in the formation of the trinuclear Pt(II) complexes [NBu4][(PPh2C6F5)(C6F5)Pt(mu-PPh2)(mu-X)Pt(mu-PPh2)2Pt(C6F5)2] [X = I (3), Br (4)] through an intramolecular PPh2/C6F5 reductive coupling and the formation of the phosphine PPh2C6F5. The trinuclear Pt(II) complex [(PPh2C6F5)(C6F5)Pt(mu-PPh2)Pt(mu-PPh2)2Pt(C6F5)2] (5), which displays two Pt-Pt bonds, can be obtained either by halide abstraction in 4 or by refluxing of 2 in CH2Cl2. This latter process also implies an intramolecular PPh2/C6F5 reductive coupling. Treatment of complex 5 with several ligands (Br-, H-, and CO) results in the incorporation of the ligand to the cluster and elimination of one (X = H-) or both (X = Br-, CO) Pt-Pt bonds, forming the trinuclear complexes [NBu4][(PPh2C6F5)(C6F5)Pt(mu-PPh2)(mu-X)Pt(mu-PPh2)2Pt(C6F5)2] [X = Br (6), H (7)] or [(PPh2C6F5)(C6F5)Pt(mu-PPh2)2Pt(mu-PPh2)(CO)Pt(C6F5)2(CO)] (8). The structures of the complexes have been established on the basis of 1H, 19F, and 31P NMR data, and the X-ray structures of the complexes 2, 3, 5, and 7 have been established. The chemical relationship between the different complexes has also been studied.     

A complete series of copper(II) halide complexes (X = F, Cl, Br, I) with a novel Cu(II)-C(sp3) bond

A complete series of copper(ii) halide complexes [CuX(tptm)](X = F (), Cl (), Br (), I (); tptm = tris(2-pyridylthio)methyl) with a novel Cu(II)-C(sp(3)) bond has been prepared by the reactions of [Cu(tptm)(CH(3)CN)]PF(6)(.PF(6)) with corresponding halide sources of KF or n-Bu(4)NX (X = Cl, Br, I), and the trigonal bipyramidal structures have been confirmed by X-ray crystallography and/or EPR spectroscopy. The iodide complex easily liberates the iodide anion in acetonitrile forming the acetonitrile complex as a result. The EPR spectra of the complexes showed several superhyperfine structures that strongly indicated the presence of spin density on the halide ligands through the Cu-X bond. The results of DFT calculations essentially matched with the X-ray crystallographic and the EPR spectroscopic results. Cyclic voltammetry revealed a quasi-reversible reduction wave for Cu(II)/Cu(I) indicating a trigonal pyramidal coordination for Cu(I) states. A coincidence of the redox potential for all [CuX(tptm)](0/+) processes indicates that the main oxidation site in each complex is the tptm ligand.     

Structural flexibility and role of vicinal 2-thienyl rings in 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], its palladium(II) complex [(CN)2Th2Pyz(PdCl2)2], and the related pentametallic pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = Mg(II)(H2O), Zn(II))

The solid state and solution structure of 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)(2)Th(2)Pyz], and its Pd(II) derivative, [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, formed by reaction of [(CN)(2)Th(2)Pyz] with [(C(6)H(5)CN)(2)PdCl(2)] were characterized by X-ray, UV-visible, (1)H and (13)C NMR, and extended X-ray absorption fine structure (EXAFS) spectral measurements. The X-ray crystal structure of [(CN)(2)Th(2)Pyz] shows the presence of one thienyl ring positioned orthogonal to the rest of the molecule, with the two vicinal thienyl rings lying orthogonal to each other in a rare arrangement. NMR studies of [(CN)(2)Th(2)Pyz] in the solid state and in solutions of dimethylformamide or dimethyl sulfoxide confirm a nonequivalence of the thienyl rings in the solid state and also in solution. EXAFS results indicate that two distinct Pd(II) coordination sites are formed at the di(2-thienyl)pyrazino moiety of [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, with identical Pd-N(pyz) (2.03(3) ?) and Pd-Cl (2.36(3) ?) bond lengths but with different Pd-S1 (2.25(4) ?) and Pd-S2 (3.21(5) ?) bond distances in an overall asymmetric molecular framework. Density functional theory (DFT) and time-dependent DFT (TDDFT) theoretical studies also provide information about the structure and spectral behavior of the precursor and its metalated Pd(II) derivative. (1)H/(13)C NMR and UV-visible spectral measurements were also carried out on two heteropentametallic porphyrazine macrocycles which were prepared by a reaction of PdCl(2) with [Th(8)TPyzPzM] where Th(8)TPyzPz = tetrakis-2,3-[5,6-di-(2-thienyl)-pyrazino]porphyrazinato dianion and M = Mg(II)(H(2)O) or Zn(II). Spectroscopic data on the newly synthesized [(PdCl(2))(4)Th(8)TPyzPzM] compounds suggest that the binding of PdCl(2) involves coordination sites of the type S(2(th))PdCl(2) with the two thienyl rings of each di(2-thienyl)pyrazino fragment bound to Pd(II) in an equivalent manner ("th-th" coordination). This is similar to what was found for the corresponding octapyridinated analogues ("py-py" coordination).     

Synthesis of eta1-borazine complexes of palladium and platinum

The eta(1)-borazine complexes trans-[(Cy(3)P)(2)M(Br)(Br(2)B(3)N(3)H(3))] (Cy = cyclohexyl) were prepared by oxidative addition of a B-Br bond of (BrBNH)(3) to [M(PCy(3))(2)] (M = Pd, Pt). Furthermore the platinum compound was converted into the T-shaped cationic complex trans-[(Cy(3)P)(2)Pt(Br(2)B(3)N(3)H(3))][BAr(f)(4)] [Ar(f) = 3,5-(CF(3))(2)C(6)H(3)] by addition of Na[BAr(f)(4)].     

Zur Reaktion der Alkin-Kupfer(I)-Komplexe [CuX(S-Alkin)] (X = Cl,Br, I; S-Alkin = 3,3,6,6-Tetramethyl-1-thia-4-cycloheptin) mit dem Chelat-Liganden N,N,N′,N′-Tetramethylethylendiamin (tmeda)

Organometallic Compounds of Copper. XVII. On the Reaction of the Alkyne-Copper(I) Complexes [CuX(S-Alkyne)] (X = Cl, Br, I; S-Alkyne = 3,3,6,6-Tetramethyl-1-thiacyclohept-4-yne) with the Chelate Ligand N,N,N′,N′-Tetramethylethylendiamine (tmeda) The alkyne copper(I) chloride complex [CuCl(S-Alkyne)]_n ( 2 a ) (S-Alkyne = 3,3,6,6–tetramethyl-1-thiacyclohept-4-yne) adds tetramethylethylene diamine (tmeda) to form the mononuclear compound [CuCl(S-Alkyne)(tmeda)] ( 4 ). The alkyne copper halide complexes [CuBr(S-Alkyne)]_n ( 2 b ) and [CuI(S-Alkyne)]_n ( 2 c ) react with tmeda to yield the complex salts [Cu(S-Alkyne)(tmeda)]⁺ [CuX₂(S-Alkyne)]^– (X = Br ( 5 a ), X = I ( 5 b )). X-ray diffraction studies on all new compounds 4 and 5 reveal distorted tetrahedral coordination of the copper atom in complex 4 and trigonal-planar coordinated copper atoms in the cations and anions of the ionic compounds 5 .     

Chemistry of nitrosyliron complexes supported by a β-diketiminate ligand

Several nitrosyl complexes of Fe and Co have been prepared using the sterically hindered Ar-nacnac ligand (Ar-nacnac = anion of [(2,6-diisopropylphenyl)NC(Me)](2)CH). The dinitrosyliron complexes [Fe(NO)(2)(Ar-nacnac)] (1) and (Bu(4)N)[Fe(NO)(2)(Ar-nacnac)] (2) react with [Fe(III)(TPP)Cl] (TPP = tetraphenylporphine dianion) to generate [Fe(II)(NO)(TPP)] and the corresponding mononitrosyliron complexes. The factors governing NO transfer with dinitrosyliron complexes (DNICs) 1 and 2 are evaluated, together with the chemistry of the related mononitrosyliron complex, [Fe(NO)Br(Ar-nacnac)] (4). The synthesis and properties of the related cobalt dinitrosyl [Co(NO)(2)(Ar-nacnac)] (3) is also discussed for comparison to DNICs 1 and 2. The solid-state structures of several of these compounds as determined by X-ray crystallography are reported.     

Cobalt(II), nickel(II), copper(II), and zinc(II) complexes with [3(5)]adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane, and [(2.3)(2).2(1)] adamanzane, 1,5,9,12-tetraazabicyclo[7.5.2]hexadecane

Isolation of the free bicyclic tetraamine, [3(5)]adamanzane.H(2)O (1,5,9,13-tetraazabicyclo[7.7.3]nonadecane.H(2)O), is reported along with the synthesis and characterization of a copper(II) complex of the smaller macrocycle [(2.3)(2).2(1)]adamanzane (1,5,9,12-tetraazabicyclo[7.5.2]hexadecane) and of three cobalt(II), four nickel(II), one copper(II), and two zinc(II) complexes with [3(5)]adamanzane. For nine of these compounds (2-8, 10b, and 12) the single-crystal X-ray structures were determined. The coordination geometry around the metal ion is square pyramidal in [Cu([(2.3)(2).2(1)]adz)Br]ClO(4) (2) and trigonal bipyramidal in the isostructural structures [Cu([3(5)]adz)Br]Br (3), [Ni([3(5)]adz)Cl]Cl (5), [Ni([3(5)]adz)Br]Br (6), and [Co([3(5)]adz)Cl]Cl (8). In [Ni([3(5)]adz)(NO(3))]NO(3) (4) and [Ni([3(5)]adz)(ClO(4))]ClO(4) (7) the coordination geometry around nickel(II) is a distorted octahedron with the inorganic ligands at cis positions. The coordination polyhedron around the metal ion in [Co([3(5)]adz)][ZnCl(4)] (10b) and [Zn([3(5)]adz)][ZnCl(4)] (12) is a slightly distorted tetrahedron. Anation equilibrium constants were determined spectrophotometrically for complexes 2-6 at 25 and 40 degrees C and fall in the region 2-10 M(-1) for the halide complexes and 30-65 M(-1) for the nickel(II) nitrate complex (4). Rate constants for the dissociation of the macrocyclic ligand from the metal ions in 5 M HCl were determined for complexes 2, 3, 5, 8, 10, and 12. The reaction rates vary from half-lives at 40 degrees C of 14 min for the dissociation of the Zn([3(5)]adz)(2+) complex (12) to 14-15 months for the Ni([3(5)]adz)Cl(+) ion (5).     

Triazenide-bridged rhodium-palladium complexes: [I2Rh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)]-, a stable paramagnetic [RhPd]4+ species with a localised Rh(II) centre

Deprotonation of mixtures of the triazene complexes [RhCl(CO)2(p-MeC6H4NNNHC6H4Me-p)] and [PdCl(eta(3)-C3H5)(p-MeC6H4NNNHC6H4Me-p)] or [PdCl2(PPh3)(p-MeC6H4NNNHC6H4Me-p)] with NEt3 gives the structurally characterised heterobinuclear triazenide-bridged species [(OC)2Rh(mu-p-MeC6H4NNNC6H4Me-p)2PdLL'] {LL' = eta(3)-C3H5 1 or Cl(PPh3) 2} which, in the presence of Me3NO, react with [NBu(n)4]I, [NBu(n)4]Br, [PPN]Cl or [NBu(n)4]NCS to give [(OC)XRh(mu-p-MeC6H4NNNC6H4Me-p)2PdCl(PPh3)]- (X = I 3-, Br 4-, Cl 5- or NCS 6-) and [NBu(n)4][(OC)XRh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)], (X = I 7- or Br 8-). The allyl complexes 7- and 8- undergo one-electron oxidation to the corresponding unstable neutral complexes 7 and 8 but, in the presence of the appropriate halide, oxidative substitution results in the stable paramagnetic complexes [NBu(n)4][X2Rh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)], (X = I 9- or Br 10-). X-Ray structural (9-), DFT and EPR spectroscopic studies are consistent with the unpaired electron of 9- and 10- localised primarily on the Rh(II) centre of the [RhPd]4+ core, which is susceptible to oxygen coordination at low temperature to give Rh(III)-bound superoxide.     

Syntheses and structures of copper(I) complexes based on Cu(n)X(n) (X = Br and I; n = 1, 2 and 4) units and bis(pyridyl) ligands with longer flexible spacer

Self-assembly of four bis(pyridyl) ligands with longer flexible spacer: 1,4-bis(3-pyridylaminomethyl)benzene (L1), 1,4-bis(2-pyridylaminomethyl)benzene (L2), 1,3-bis(3-pyridylaminomethyl)benzene (L3) and 1,3-bis(2-pyridylaminomethyl)benzene (L4), and CuX (X = Br and I) leads to the formation of eight [Cu(n)X(n)]-based (X = Br and I; n = 1, 2, and 4) complexes, [Cu(2)I(2)L1(PPh(3))(4)] (1), [Cu(4)Cl(2)Br(2)(L4)(2)(PPh(3))(6)]·(CH(3)CN)(2) (2), [Cu(2)I(2)(L3)(2)] (3), {[Cu(2)Br(2)L2(PPh(3))(2)]·(CH(2)Cl(2))(2)}(n) (4), [CuIL1](n)·nCH(2)Cl(2) (5), [CuIL1](n) (6), [CuIL4](n) (7) and [Cu(2)I(2)L4](n) (8), which have been synthesized and characterized by elemental analysis, IR, TG, powder and single-crystal X-ray diffraction. Structural analyses show that the eight complexes possess an increasing dimensionality from 0D (1-3) to 1D (4) to 2D (5-8), in which 1 and 2 contain a CuX unit, 2-7 contain a Cu(2)X(2) unit and 8 contains a Cu(4)X(4) unit. Such evolvement indicates that the conformation of flexible bis(pyridyl) ligands and the participation of triphenylphosphine (PPh(3)) as a second ligand take an essential role in the framework formation of the Cu(i) complexes. Moreover, a pair of symmetry-related L3 ligands in complex 3 coordinate to the rhomboid Cu(2)I(2) dimer to form "handcuff-shaped" dinuclear structures, which are further joined together through intermolecular N-HI hydrogen bonds to furnish a 2D (4,4) layer. Although complexes 5 and 6 exhibit a similar 2D (4,4) layer constructed from L1 ligand bridging [Cu(2)I(2)](n) units, the different packing fashion of the layers leads to the formation of 3D porous frameworks of 5 and dense 3D frameworks of 6. The "twisted-boat" conformation of the Cu(4)I(4) tetramer unit in complex 8 has not been reported so far.     

Copper halide-bridged ruthenium telluride carbonyl complexes: discovery of the semiconducting cluster chain polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2].THF}infinity

A new series of Te-Ru-Cu carbonyl complexes was prepared by the reaction of K(2)TeO(3) with [Ru(3)(CO)(12)] in MeOH followed by treatment with PPh(4)X (X=Br, Cl) and [Cu(MeCN)(4)]BF(4) or CuX (X=Br, Cl) in MeCN. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was first treated with PPh(4)X followed by the addition of [Cu(MeCN)(4)]BF(4), doubly CuX-bridged Te(2)Ru(4)-based octahedral clusters [PPh(4)](2)[Te(2)Ru(4)(CO)(10)Cu(2)X(2)] (X=Br, [PPh(4)](2)[1]; X=Cl, [PPh(4)](2)[2]) were obtained. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)X (X=Br, Cl) followed by the addition of CuX (X=Br, Cl), three different types of CuX-bridged Te-Ru carbonyl clusters were obtained. While the addition of PPh(4)Br or PPh(4)Cl followed by CuBr produced the doubly CuBr-bridged cluster 1, the addition of PPh(4)Cl followed by CuCl led to the formation of the Cu(4)Cl(2)-bridged bis-TeRu(5)-based octahedral cluster compound [PPh(4)](2)[{TeRu(5)(CO)(14)}(2)Cu(4)Cl(2)] ([PPh(4)](2)[3]). On the other hand, when the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te(2)Ru(4)-based octahedral cluster chain polymer {[PPh(4)](2)(Te(2)Ru(4)(CO)(10)Cu(4)Br(2)Cl(2)).THF}(infinity) ({[PPh(4)](2)[4].THF}(infinity)) was produced. The chain polymer {[PPh(4)](2)[4].THF}(infinity) is the first ternary Te-Ru-Cu cluster and shows semiconducting behavior with a small energy gap of about 0.37 eV. It can be rationalized as resulting from aggregation of doubly CuX-bridged clusters 1 and 2 with two equivalents of CuCl or CuBr, respectively. The nature of clusters 1-4 and the formation and semiconducting properties of the polymer of 4 were further examined by molecular orbital calculations at the B3LYP level of density functional theory.