Dihalomethanes as Bent Bifunctional XB/XB‐Donating Building Blocks for Construction of Metal‐involving Halogen Bonded Hexagons

The dihalomethanes CH₂X₂ (X=Cl, Br, I) were co‐crystallized with the isocyanide complexes trans‐[MX^M₂(CNC₆H₄‐4‐X^C)₂] (M=Pd, Pt; X^M=Br, I; X^C=F, Cl, Br) to give an extended series comprising 15 X‐ray structures of isostructural adducts featuring 1D metal‐involving hexagon‐like arrays. In these structures, CH₂X₂ behave as bent bifunctional XB/XB‐donating building blocks, whereas trans‐[MX^M₂(CNC₆H₄‐4‐X^C)₂] act as a linear XB/XB acceptors. Results of DFT calculations indicate that all XCH₂–X???X^M–M contacts are typical noncovalent interactions with estimated strengths in the range of 1.3–3.2 kcal mol^?1. A CCDC search reveals that hexagon‐like arrays are rather common but previously overlooked structural motives for adducts of trans‐bis(halide) complexes and halomethanes.     

Mixed dimethyl sulfoxide-thiocarbamic ester complexes of platinum(II) halides

Summary The platinum(II) halidecis-[Pt(DMTC)(DMSO)X₂] andcis-[Pt(DETC)(DMSO)X₂](X=Cl or Br; DMSO=dimethyl sulfoxide; DMTC=EtOSCN-Me₂; DETC=EtOSCNEt₂) adducts and the platinum(II) and palladium(II) halide adducts,trans-[M(DETC)₂X₂] (M=Pt or Pd; X=Cl or Br), have been prepared. The complexes were characterized by i.r., and¹H and¹³Cn.m.r. spectroscopy. Both DMTC and DETC coordinate through the sulphur atoms. The 1:2 DETC complexes present the usualtrans configuration, whereas the presence of DMSO favourscis geometry in the mixed species.     

The infrared spectra of imidazole complexes of platinum(II) halides and nitrite

Summary The i.r. spectra (4000-90 cm^–1) of the [Pt(Him)₄]X₂ complexes (Him = imidazole, X = Cl, Br or I) andcis- andtrans-[Pt(Him)₂X₂] (X = Cl, Br, I or NO₂) and their D₃-labelled analogues have been determined. The distinction between the ring and C-H (or N-H) modes of imidazole is based on the relative shifts which these bands undergo on D₃-labelling. Assignments, based on the effects of imidazole deuteriation and halide substitution, are provided for the v(Pt-Him) and v(Pt-X) modes.     

Co-ordination compounds of diacetyldihydrazone and diacetylbis(monomethylhydrazone)

Summary Diacetyldihydrazone (DADH) forms only six-coordinate complexes with iron(II), cobalt(II), nickel(II) and zinc(II). In M(DADH)₂X₂ (M=Fe, X=Br or I; M=Co, X=I; M=Ni, X=Cl, Br or NCS) the ligand is chelating in the [M(DADH)₃]²⁺ cations, while in M(DADH)₂X₂ (M=Co, X=Cl or Br; M=Ni, X=Cl or Br) the ligand is probably bridging and bidentate. Diacetylbismonomethylhydrazone (DAMH), by contrast, forms predominantly tetrahedral complexes M(DAMH)X₂ (M=Fe or Co, X=Cl or Br; M=Ni, X=Br; M=Co, X=NCS; M=Zn, X=Cl, Br or NCS) and some octahedral complexes M(DAMH)₂X₂ (M=Co, X=NCS; M=Ni, X=Br). The i.r. spectra, electronic spectra and magnetic moments of the complexes are discussed.     

Complexes of 8-Aminoouinoline. II. The Infrared Spectra of the Bisand Mono(Aminoquinoline) Complexes of Metal(II) Halides

Abstract

The infrared spectra of the complexes M(aq)₂(H₂O)₂X₂ (M = Fe, Co, Ni, Cu; aq = 8-aminoquinoline; X =Cl, Br) have been determined over the range 4000-50 cm^?1. Absence of vM-X bands indicates that the halide is not coordinated to the metal ion and the complexes are correctly formulated [M(aq)₂-(H₂O)₂]X₂. Deuteration of the amino group and the effects of metal ion substitution enable assignment of the vM-NH₂, vM-N and vM-OH₂ modes as well as the amino group vibrations. ¹⁸ O-Labelling assists in identifying the vO-H, vO-H……X and δO-H bands. The spectra are consistent with trans-octahedral coordination and axial bonding of the water molecules. The far infrared spectra of the mono(aminoquinoline) complexes [M(aq)X₂]_n (M = Cu, Zn; X = Cl, Br) are consistent with the proposed structure of polymeric octahedral coordination involving both bridging and terminal M-X bonds. The vM-NH₂, vM-N, vM-X(terminal) and vM-X(bridging) bands are assigned by studying the effects of amino group deuteration, metal ion substitution and halide substitution.     

Synthesis and structural characterization of 3d-metal complexes of pyridine-4-carboxaldehyde thionicotinoyl hydrazone

Summary Pyridine-4-carboxaldehyde thionicotinoyl hydrazone (4-PTNH) forms 1:1 adducts with metal(II) halides and 1:2 complexes (metal to ligand) with metal(II) thiocyanates. Magnetic and spectral studies indicate polymeric octahedral geometry for M(4-PTNH)X₂ (M=Co^II or Cu^II, X=Cl; M=Ni^II, X=Cl, Br or I), five coordinate geometry for Co(4-PTNH)X₂ (X=Br or I) and octahederal geometry for [M(4-PTNH)₂(NCS)₂] (M=Co^II or Ni^II). I.r. spectral studies show that 4-PTNH acts as a neutral bidentate ligand in all the complexes, the bonding sites being the thione sulphur and azomethine nitrogen.     

Four-Center Nodes: Supramolecular Synthons Based on Cyclic Halogen Bonding

The isocyanide trans-[PdBr₂(CNC₆H₄-4-X′)₂] (X′=Br, I) and nitrile trans-[PtX₂(NCC₆H₄-4-X′)₂] (X/X′=Cl/Cl, Cl/Br, Br/Cl, Br/Br) complexes exhibit similar structural motif in the solid state, which is determined by hitherto unreported four-center nodes formed by cyclic halogen bonding. Each node is built up by four Type II C−X′⋅⋅⋅X−M halogen-bonding contacts and include one Type I M−X⋅⋅⋅X−M interaction, thus giving the rhombic-like structure. These nodes serve as supramolecular synthons to form 2D layers or double chains of molecules linked by a halogen bond. Results of DFT calculations indicate that all contacts within the nodes are typical noncovalent interactions with the estimated strengths in the range 0.6–2.9 kcal mol⁻¹.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. IX. Preparation and 1H-NMR. Studies of complexes [MX2(1)] and [M′Cl(CO)(1)] (M = Pd,Pt; M′ = Rh,Ir; X = Cl,Br, I; 1 = 2, 11-Bis-(diphenylarsinomethyl)benzo[c]phenanthrene) and crystal and molecular structure of [PtCl2(1)]

The preparation of the bidentate ligand 2, 11-bis(diphenylarsinomethyl)benzo-[c]-phenanthrene ( 1 ) is described. This ligand reacts with appropriate substrates to give mononuclear square planar complexes of type [MX₂( 1 )] (M = Pd, Pt; X = Cl, Br, I) and [M′Cl(CO)( 1 )] (M′ = Rh, Ir) in which ligand 1 spans trans-positions. This is confirmed by the crystal structure of [PtCl₂( 1 )]. ¹H-NMR. spectra of the complexes are discussed and compared with those of model compounds trans-[MCl₂( 12 )₂] (M = Pd, Pt) and [M'Cl(CO)( 12 )₂] (M′ = Rh, Ir; 12 = AsBzPh₂).     

Complexes with furan oximes. Part III. Synthesis and characterization of 3-(2-furyl) 2-propene aldoxime and 3-(5-methyl 2-furyl) 2-propene aldoxime complexes with 3d element dihalides

Summary 3-(2-Furyl) 2-propene aldoxime (FAOH) and 3-(5-methyl 2-furyl) 2-propene aldoxime (M5FAOH) react, in stoichiometric amounts, with 3d divalent metal halides MX₂(M=Mn, Co, Ni, Cu and Zh; X=Cl or Br) to givetrans-octahedral complexes, except the ZnCl₂ derivative with FAOH which is tetrahedral. These ligands are bidentate in [ML₂X₂] species (L=FAOH or M5FAOH) through the cyclic oxygen atom and the oxime nitrogen, and are monodentate for [ML₄X₂] complexes and [ZnCl₂(FAOH)₂] through the N-oxime atom. The structures were established by analytical and spectroscopic data.     

Complexes of group IIb metals with dithio oxamides—II. Vibrational analysis of ZnLX2(X = Cl,Br, I) complexes

With dithiooxamides, Zn(II) in acid media forms distorted tetrahedral complexes, which behave as non-electrolytes. The ligands act as bidentates with S, S coordination.A thorough vibrational analysis has been performed for the Zn(CH₃ NHCSCSNHCH₃)X₂(X = Cl, Br, I) and for the Zn[(CH₃)₂NCSCSN(CH₃)₂]X₂(X = Cl, Br, I) complexes.     

Rhenium,part XIV. Studies on the action of hydrogen halides on [ReO2en2]+

Summary The products from the reaction oftrans-dioxobis(ethylenediamine)rhenium(V) halides with hydrogen halides have been investigated. Dilute (2M) and concentrated hydrochloric acid react with (ReO₂en₂)Cl in the cold to give ReO(OH)enCl₂ and IRe(OH)₂enCl₂]Cl respectively, while with hot 6M HCl [ReOCl₅]^2– is formed. Dilute solutions of HX protonate [ReO₂en₂]X (X = Br and I) giving [ReO(OH)en₂]X₂ which are converted slowly into ReO(OH)enBr₂ and [ReO(OH)en2](I₃)₂. Hot and concentrated solutions of HX reduce Re^v in (ReO₂en2 )X (X = Br and I) giving enH₂(ReBr₆) and ReI₄en. The thermal decomposition of (ReO₂en₂)X (X = Cl, Br and I) has been studied by thermogravimetry and a polymeric compound, Re₂O₇en₂, has been isolated by heating (ReO₂en₂)X at 200°. The compounds have been characterised by molecular conductivities, magnetic susceptibility and i.r. spectra.     

The infrared spectra (3500—150 cm-1) of aniline complexes of cobalt(II), nickel(II), copper(II) and zinc(II) halides

The IR spectra (3500—150 cm^?1) of the complexes [M(aniline)₂,X₂ (M = Co, Ni, Cu, Zn; X = Cl, Br), [Zn(aniline)₂I₂] are discussed. Assignments of the internal ligand vibrations are based on the band shifts which result from ¹⁵N-labelling of the amino group. The metal—ligand stretching frequencies, ν(M—N) and ν(M—X), are assigned on the basis of the band shifts which occur on ¹⁵N-labelling and metal ion and halogen substitution. Two bands within the range 350–450 cm^?1 are assigned to ν(M—N) while the ν(M—X) bands occur within the range 170–320 cm^?1. The effects of structure and coordination number on ν(M—N) and ν(M—X) are discussed. The spectra of two ethanol adducts, [M(aniline)₂-(ethanol)₂Cl₂] (M = Co, Ni) compared with those of the unsolvated species [M(aniline)₂-Cl₂], exhibit a unique band near 480 cm^?1 which is insensitive to ¹⁵N-labelling and is assigned to ν(M—O).     

Gemischtligandkomplexe des Rheniums. V. Die Bildung von Nitrenkomplexen durch Kondensation von Aceton an koordinierten Nitridoliganden. Darstellung und Strukturen von fac-[Re{NC(CH3)2CH2C(O)CH3}X3(Me2PhP)2]-Komplexen (X = Cl,Br)

Mixed-ligand Complexes of Rhenium. V. The Formation of Nitrene Complexes by Condensation of Acetone at Coordinated Nitrido Ligands. Syntheses and Structures of fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] Complexes (X = Cl, Br) The reaction of rhenium(V)-mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] (HR₂tcb = N? (N,N-dialkylthiocarbamoyl)benzamidine) with HCl or HBr in acetone initializes a condensation of the solvent and results in nitrene-like compounds as a consequence of a nucleophilic attack of the coordinated nitrido ligand on the condensed acetone. The chelate ligands are removed during this reaction and complexes of the type fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] (X = Cl, Br) are formed. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] crystallizes triclinic in the space group P1, a = 8.575(4); b = 9.088(3); c = 18.389(9) Å; α = 75.67(3)°, β = 85.30(3)°, γ = 70.58(4)°; Z = 2. A final R value of 0.031 was obtained on the basis of 6011 independent reflections with I ≥ 2σ(I). Rhenium is coordinated in a distorted octahedral environment with the three chloro ligands in facial positions. The rhenium-nitrogen bond (1,68(1) Å) is only slightly longer than typical Re? N bonding distances in nitrido complexes. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] is isomorphous with the chloro complex. Triclinic cell with a = 8.625(4); b = 9.198(3); c = 18.581(5) Å; α = 75.62(3)°, β = 85.40(3)°, γ = 70.91(3)°; Z = 2. The R value converged at 0.049 on the basis of 3644 independent reflections with I ≥ 2σ(I). fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] as well as fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] crystallizes in the noncentrosymmetric space group P1.     

Complexes of palladium,platinum and rhodium with 2,2′-biquinoline and 2-(2′-pyridyl)quinoline

Summary The reactions of 2,2-biquinoline(biq) with M(PhCN)₂X₂ (M=Pd; X=Cl or Br; M=Pt, X=Cl, Br or I), K₂PtCl₄ and RhCl₃·3H₂O and of 2-(2-pyridyl)quinoline (pq) with K₂PtCl₄ and RhCl₃·3H₂O have been investigated. The isolated complexescis-[Pd(biq)X₂] (X=Cl or Br),cis-[Pt(biq)Cl₂],cis-[Pt(biq)Cl₂]·H₂O,trans-[Pt(biq)₂Br₂]·5H₂O, [Pt₃(biq)₂I₆],mer-[Rh(biq)Cl₃-(H₂O)] andmer-[Rh(pq)Cl₃(H₂O)] have been characterized by elemental analyses, conductivity measurements, i.r., electronic, and¹H n.m.r. spectra. The reaction of pq with K₂PtCl₄ in 1M H₂SO₄ gave the salt 2-(2-pyridyl) quinolinium tetrachloroplatinate(II) pentahydrate, (pqH)₂[PtCl₄]·5H₂O; when the reaction was carried out in aqueous acetone,cis-[Pt(pq)Cl₂] was obtained. A new method for the synthesis ofcis-[Rh(biq)₂X₂]X (X=Cl or Br) is described; both compounds have been further characterized by¹H n.m.r.     

Transition metal complexes with bidentate ligands spanning trans-positions. IV. Preparation and properties of some rhodium and iridium complexes of 2,11-bis(diphenylphosphinomethyl)benzo [c]phenanthrene

The bidentate phosphine 2,11-bis(diphenylphosphinomethyl)benzo [c]phenanthrene ( 1 ) has been used to prepare the mononuclear, square planar complexes trans-[MX(CO)( 1 )] and trans-[M(CO)(CH₃CN)( 1 )][BF₄] (M = Rh, Ir; X = Cl, Br, I, NCS). It is found that the tendency of these complexes to form adducts with CO, O₂ and SO₂ is significantly lower than that of the corresponding Ph₃P complexes. The oxidative-addition reactions of complexes trans-[IrX (CO) ( 1 )] with hydrogen halides give the six-coordinate species [IrHX₂(CO) ( 1 )]. The complexes [IrH₂I (CO) ( 1 )] and [IrH₂L (CO) ( 1 )] [BF₄] (L = CO and CH₃CN) have been obtained from hydrogen and the corresponding substrates. The model compounds trans-[MCl (CO) (Ph₂PCH₂Ph)₂] (M = Rh, Ir), trans-[Ir (CO) (CH₃CN) (Ph₂PCH₂Ph)₂] [BF₄], [IrHCl₂(CO)(Ph₂PCH₂Ph)₂] and [IrH₂(CO)₂(Ph₂PCH₂Ph)₂] [BF₄] have been prepared and their special parameters are compared with those of the corresponding complexes of ligand 1 . The influence of the static requirements of this ligand on the chemistry of its rhodium and iridium complexes is discussed.     

Density functional theory study on the reactions of X− with CH3SY (X,Y = F,Cl, Br,I)

Gas‐phase anionic reactions X^? + CH₃SY (X, Y = F, Cl, Br, I) have been investigated at the level of B3LYP/6‐311+G (2df,p). Results show that the potential energy surface (PES) of gas‐phase reactions X^? + CH₃SY (X, Y = Cl, Br, I) has a quadruple‐well structure, indicating an addition–elimination (A–E) pathway. The fluorine behaves differently in many respects from the other halogens and the reactions F^? + CH₃SY (Y = F, Cl, Br, I) correspond to deprotonation instead of substitution. The gas‐phase reactions X^? + CH₃SF (X = Cl, Br, I), however, follow an A–E pathway other than the last two out going steps (COM2 and PR) that proceeds via a deprotonation. The polarizable continuum model (PCM) has been used to evaluate the solvent effects on the energetics of the reactions X^? + CH₃SY (X, Y = Cl, Br, I). The PES is predicted to be unimodal in the solvents of high polarity. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Transition metal chemistry of oxime — Containing ligands,Part XXVIII; manganese(II) complexes of 2,6-diacetylpyridine dioxime

Summary Complexes of manganese(II) with the tridentate oxime ligand 2,6-diacetylpyridine dioxime (H₂dapd) have been synthesized and characterized. The complexes [Mn(H₂dapd)X₂] are pentacoordinate for X = Cl, Br or I but apparently octahedralvia bridging anions for X = NCS or NCSe. The complex [Mn(H₂dapd)(NO₃)₂] adopts an octahedral structure involving monodentate and bidentate coordination of nitro groups. The complexes [Mn(H₂dapd)₂]X₂ (X = Cl, Br, I, NO₃, NCS or NCSe) involve an octahedral cation.     

Structural and Infrared Spectroscopic Studies of Some Adducts of Divalent Metal Dihalides (MX2, M = Zn,Cd; X = CI,Br, I) with Variously Hindered Monodentate Nitrogen (Pyridine) Base Ligands (L = Pyridine, 2‐Methylpyridine,and Quinoline) of 1:2 Stoichiometry

Single crystal X‐ray structure determinations are described for a number of adducts of 1:2 MX₂:L stoichiometry, [M = divalent metal (Zn, Cd); X = halide (Cl, Br, I), L = (variously hindered) monodentate nitrogen (pyridine) base: py = pyridine, 2‐mpy = 2‐methylpyridine, quin = quinoline]: [(2‐mpy)₂ZnX₂] (X = Cl, Br) (isotypic, triclinic P , a ≈? 7.9₆, b ≈? 8.7, c ≈? 11.4 Å, α ≈? 86, β ≈? 79.3, γ ≈? 67°, Z = 2), [(2‐mpy)₂ZnI₂], [(quin)₂ZnX₂] (X = Br) (isotypic with the previously determined chloride, X = Cl, triclinic, P , a ≈? 8.7, b ≈? 9.6, c ≈? 11.1 Å, α ≈? 81, β ≈? 73, γ ≈? 72°, Z = 2); [(quin)₂ZnI₂]; [(2‐mpy)₂CdX₂], X = Br {isotypic with [(2‐mpy)₂ZnX₂], X = Cl, Br (above)}, X = I {isotypic with [(2‐mpy)₂ZnI₂] (above)}; [(quin)₂CdI₂]. A single molecule, with a four‐coordinate quasi‐tetrahedral metal atom, N₂MX₂, comprises the asymmetric unit of the structure in each of these. A one‐dimensional polymer is found for [(quin)₂Cd(μ‐Cl)₂]_(∞‖∞), similar to those recorded previously for CdX₂:py (1:2) (X = Cl, Br, I), the cadmium atom here lying on a 2‐axis in tetragonal space group P 2₁c, and the quin ligands coordinating trans in a six‐coordinate array about the cadmium, with successive cadmium atoms being linked by pairs of bridging chlorines. Adducts of MX₂:L (1:1) stoichiometry, defined for M = Cd: [(2,4,6‐trimethylpyridine)Cd(μ‐I)₂]_(∞‖∞) and [(quin)Cd(μ‐Br)₂]_(∞‖∞), are both infinite one‐dimensional polymers … (μ‐X)₂Cd(L)(μ‐X)₂Cd(L) … , with five‐coordinate trigonal bipyramidal cadmium atoms, the nitrogen donors being equatorial in the coordination spheres. The far‐IR spectra of [L₂MX₂] (L = py, 2‐mpy, quin; M = Zn, Cd; X = Cl, Br, I) are assigned and discussed in relation to the structures of the complexes.     

Preparation,Structural Characterization,and Antifungal Activities of Complexes of Group 12 Metals with 2‐Acetylpyridine‐ and 2‐Acetylpyridine‐N‐oxide‐4N‐phenylthiosemicarbazones

Reaction of group 12 metal dihalides in ethanolic media with 2‐acetylpyridine ⁴N‐phenylthiosemicarbazone ( H4PL ) and 2‐acetylpyridine‐N‐oxide ⁴N‐phenylthiosemicarbazone ( H4PLO ) afforded the compounds [M(H4PL)X₂] (X = Cl, Br, M = Zn, Cd, Hg; X = I, M = Zn, Cd) ( 1–8 ), [Hg(4PL)I]₂ ( 9 ) and [M(H4PLO)X₂] (X = Cl, Br, I, M = Zn, Cd, Hg) ( 10–18 ). H4PL , H4PLO and their complexes were characterized by elemental analysis and by IR and ¹H and ¹³C NMR spectroscopy (and the cadmium complexes by ¹¹³Cd NMR spectroscopy), and H4PL , H4PLO , ( 5 · DMSO) and ( 9 ) were additionally studied by X‐ray diffraction. H4PL is N,N,S‐tridentate in all its complexes, including 9 , in which it is deprotonated, and H4PLO is in all cases O,N,S‐tridentate. In all the complexes, the metal atoms are pentacoordinate and the coordination polyhedra are redistorted tetragonal pyramids. In assays of antifungal activity against Aspergillus niger and Paecilomyces variotii, the only compound to show any activity was [Hg(H4PLO)I₂] ( 18 ).     

Synthesis and characterization of Ru(III), Rh(III), Pt(IV) and Ir(III) thiosemicarbazone complexes

Ru(III), Rh(III), Pt(IV) and Ir(III) complexes of 2-furfural thiosemicarbazone as ligand have been synthesised. These complexes have the composition [M(ligand)₂X₂]X (M = Ru(III) Rh(III) and Ir(III) X = Cl and Br) and [Pt(ligand)₂ X₂] X₂ (X = Cl, Br and 1/2SO₄). The deprotonated ligand forms the complexes of the formulae M(ligand-H)₃ and Pt(ligand-H)₃Cl. All these complexes have been characterized by elemental analysis, magnetic measurements, electronic and infrared spectral studies. All the complexes are six-coordinate octahedral.