Intra- and inter-ion-pair protonic-hydridic bonding in polyhydridobis(phosphine)rhenates

2001 ◽  
Vol 79 (5-6) ◽  
pp. 964-976 ◽  
Author(s):  
Kamaluddin Abdur-Rashid ◽  
Alan J Lough ◽  
Robert H Morris

The hexahydridobis(phosphine)rhenate anions, [ReH6(PR3)2]- (PR3 = PCy3, P-i-Pr3, PPh3, PMe3) were generated by potassium hydride deprotonation of the neutral heptahydride conjugate acids (ReH7(PR3)2), isolated as their [K(18-crown-6)]+ and [K(1,10-diaza-18-crown-6)]+ salts, and characterized by NMR and IR spectroscopy and elemental analyses. Structures from single crystal X-ray diffraction were obtained for the [K(1,10-diaza-18-crown-6)]+salts and these indicate the presence of short protonic—hydridic bonds involving the hydrides of the anions and the proton donor NH moieties of the cations. The structure of [K(1,10-diaza-18-crown-6)][ReH6(P-i-Pr3)2] adopts a one-dimensional zigzag chain with alternating cations and anions connected and held together by inter-ion N-H···Hx-Re interactions (x = 1 or 2). Short distances between the NH protons of the cations and hydrides of the anion ranging from 1.6 to 1.9 Å are estimated for this complex. A different kind of chain structure is observed for [K(1,10-diaza-18-crown-6)][ReH6(PMe3)2] in which the combined effects of inter-ion protonic—hydridic bonding (N-H···Hx-Re) and inter-ion electrostatic interactions (ReH-x···K+···H-xRe), result in one-dimensional networks of alternating cations and anions, with the metals and hydrides occupying the interior and the organic moieties of the phosphine ligands and crown ether lining the exterior of cylindrical supramolecular assemblies. A combination of intra- and inter-ion protonic-hydridic and intra-ion-pair electrostatic interactions in [K(1,10-diaza-18-crown-6)][ReH6(PPh3)2] result in the formation of discrete two-dimensional {[K(1,10-diaza-18-crown-6)][ReH6(PPh3)2]}4 tetramers. The PCy3 salt is disordered but appears to consist of isolated 1:1 ion pairs containing strong intra-ion-pair NH···HRe bonding. The solid-state IR spectra of the [K(1,10-diaza-18-crown-6)]+ salts show low-frequency shifts for the NH bands relative to [K(1,10-diaza-18-crown-6)][BPh4], and perturbed Re-H bands relative to those in the [K(18-crown-6)]+ salts. The magnitude of ΔνNH is related to the basicity of the anion as indicated by the pKαTHF of the conjugate acid form (ReH7(PR3)2), which increases as PPh3 < < PMe3 < P-i-Pr3 < PCy3. Solution 1H NMR, NOE, and T1 relaxation measurements of [K(1,10-diaza-18-crown-6)][ReH6(PPh3)2] indicate that these interactions also persist in toluene solutions of this compound.Key words: rhenium, hydride, phosphine, hydrogen bonding, self-assembly.

2003 ◽  
Vol 56 (11) ◽  
pp. 1167 ◽  
Author(s):  
Ruihu Wang ◽  
Maochun Hong ◽  
Weiping Su ◽  
Rong Cao ◽  
Yingjun Zhao ◽  
...  

Two silver(I) organosulfur coordination polymers, {[Ag2(mbpsq).dmf](NO3)2}n (1) and {[Ag3(bpsp)2(CH3CN)]-(BF4)3.2 H2O}n (2), were prepared by self-assembly of silver(I) with the chelating heterocyclic ligands mbpsq and bpsp (mbpsq = 2,3-bis[2-(4-methylpyrimidinyl)methylsulfanyl]-quinoxaline; bpsp = 2,6-bis[(2-pyrimidinyl)-methylsulfanyl]-pyridine). Single-crystal X-ray diffraction analysis reveals that (1) crystallizes in the triclinic space group P1– with a 10.1937(8), b 11.2160(9), c 13.8445(11) Å, α 103.0620(10), β 106.4850(10), γ; 96.2720(10)°, V 1452.8(2) Å3, Z 2. Each mbpsq molecule acts as a hexadentate ligand, in which two nitrogen atoms of the quinoxaline ring and adjacent sulfur atoms form two stable five-membered rings and two nitrogen atoms from different methylpyrimidine rings bridge two silver(I) centers to form a one-dimensional chain structure. Complex (2) crystallizes also in the triclinic space group P1– with a 12.8119(3), b 13.8902(4), c 15.4534(5) Å, α 70.6980(10), β 68.7570(10), γ; 85.3380(10)°, V 2416.83(12) Å3, Z 2. The bpsq molecules act as tridentate and tetradentate ligands ligating three silver(I) centres of different coordination environments to form a one-dimensional zigzag chain.


2021 ◽  
Author(s):  
Heyi Zhang ◽  
Fangyuan He ◽  
Xiaonan Li ◽  
Zhi-Hui Wang ◽  
Hong Zhang

Through the self-assembly of 1,1'-bis(3-cyanobenzyl)-[4,4'-bipyridine] dichloride ligand, m-H2BDC and Zn(NO3)2·6H2O, a novel one-dimensional chain structure multifunctional coordination polymer was successfully synthesized. Due to electron transfer during irradiation and heating to...


2014 ◽  
Vol 70 (6) ◽  
pp. 603-605 ◽  
Author(s):  
Xiu-Dan Shao ◽  
Chun-Hua Yu

An organic–inorganic hybrid compound,catena-poly[bis(3H-imidazol-1-ium) [[tetracyanido-κ4C-cobalt(III)]-μ-cyanido-κ2C:N-[diaqualithium(I)]-μ-cyanido-κ2N:C]], {(C3H5N2)2[CoLi(CN)6(H2O)2]}n, was synthesized by the reaction of Li3[Co(CN)6] with imidazolium chloride in aqueous solution. The compound crystallizes in the monoclinic space groupC2/c(data collected at 273 K). In the crystal structure, neighbouring [Co(CN)6]3−anionic units are linked by Li+cations through the cyanide groups in atransmode, forming a one-dimensional zigzag chain structure extending along thecaxis. A three-dimensional supramolecular network is formed through hydrogen-bonding interactions and is further stabilized by weak CN...π interactions between the cyanide groups and the imidazolium cations.


2008 ◽  
Vol 607 ◽  
pp. 94-98
Author(s):  
Atsuo Kawasuso ◽  
Yuki Fukaya ◽  
M. Hashimoto ◽  
Ayahiko Ichimiya ◽  
H. Narita ◽  
...  

In this work, we studied a few surfaces, of which the structures have not yet been revealed, using reflection high-energy positron diffraction (RHEPD). We studied the Ge(111)/Pb and Ge(111)/Sn surfaces that exhibit the phase transition from 3×3 to √3×√3 periodicities at around 200K. We found that in both phases the equilibrium positions of Pb and Sn adatoms are conserved. That is, in the unit-cell, one of three adatoms is located upper position and two of them are located lower positions (one-up-two-down). The phase transition is interpreted in terms of an order-disorder type. We furthermore studied the quasi-one dimensional Si(111)/In surface which exhibits the metal-insulator transition at around 120K. The high temperature phase is well explained as the zigzag chain structure. We found that a dynamic atomic displacement which leads to the formation of hexagon structure occur below 120 K. We confirmed the appearance of the band gap using the surface structure determined from the RHEPD rocking curves.


2013 ◽  
Vol 69 (11) ◽  
pp. 1332-1335 ◽  
Author(s):  
Xiu-Hua Zhao ◽  
Ya-Yun Zhao ◽  
Jie Zhang ◽  
Jian-Guo Pan ◽  
Xing Li

catena-Poly[[[4-amino-N-(quinoxalin-2-yl)benzenesulfonamidato]aquacadmium(II)]-μ-4-amino-N-(quinoxalin-2-yl)benzenesulfonamidato], [Cd(C14H11N4O2S)2(H2O)], has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction, elemental analysis, fluorescence, IR and thermal analysis. Single-crystal X-ray analysis reveals that the complex is a one-dimensional zigzag chain structure, and the CdIIcation has a distorted octahedral coordination geometry formed by five N atoms from three different sulfaquinoxaline ligands and one O atom from a water molecule. The fluorescence spectrum reveals that the complex emits strong blue fluorescence and thermal analysis shows that the complex has high thermal stability.


2005 ◽  
Vol 19 (15n17) ◽  
pp. 2757-2762 ◽  
Author(s):  
Y. ZHANG ◽  
R. SHI ◽  
H. Q. XIONG ◽  
Y. ZHAI ◽  
Y. K. SUN

Magnetite chains of spheres with different radii and lengths were prepared by aging ferrous hydroxide gel with 0.2M KNO3 under different external magnetic fields which induced the ultra-fine magnetite particles to combine into chain structure. The magnetite particle size and the chain length could be adjusted by varying the field intensity. The chains could be deposited on silicon substrates to form aligned structure in magnetic field. The hysteresis loops were measured in different directions by a vibrating sample magnetometer (VSM). The structure and magnetic properties were discussed.


2007 ◽  
Vol 63 (11) ◽  
pp. m2846-m2847 ◽  
Author(s):  
Yun Jie Wang ◽  
Hao Hong Li ◽  
Zhi Rong Chen ◽  
Chang Cang Huang ◽  
Ji Bo Liu

The title compound, {(C8H12N)[AgI2]} n , was synthesized by a self-assembling reaction of 1-ethyl-4-methylpyridinium iodide and silver(I) iodide. The anion adopts a one-dimensional chain structure with the Ag atom in the chain in a nearly regular tetrahedral environment. The crystal packing is stabilized by electrostatic interactions and by a C—H...I hydrogen bond between a methylene H atom of the ethyl substituent and an I atom.


2007 ◽  
Vol 63 (3) ◽  
pp. m842-m844
Author(s):  
Wei-Wei Fu ◽  
Zhong-Ning Chen

The reaction between [Cu2(μ-dppm)2(MeCN)2](ClO4)2 and (Bu4N)2[Mo(mnt)3], where dppm is bis(diphenylphosphino)methane and mnt is cis-1,2-dicyanoethylene-1,2-dithiolate, gave the title compound, catena-Poly[[[acetonitrilebis[μ-bis(diphenylphosphino)methane-κ2 P:P′]dicopper(I)]-μ-(1,2-dicyanoethylene-1,2-dithiolato)-[(1,2-dicyanoethylene-1,2-dithiolato)molybdenum(IV)]-μ-(1,2-dicyanoethylene-1,2-dithiolato)] diethyl ether disolvate acetonitrile solvate]. The binding between a Cu atom of the binuclear copper unit [Cu2(μ-dppm)2(MeCN)]2+ and two N atoms of the building block [Mo(mnt)3]2− results in the formation of a one-dimensional zigzag chain structure.


2012 ◽  
Vol 554-556 ◽  
pp. 268-272
Author(s):  
Jia Gui Li ◽  
Wan Ren Zhu ◽  
Shu Hong Ding ◽  
Yuan Chen ◽  
Yu Lin Zhu ◽  
...  

A new one-dimensional [CuC16H18N4O4S]n(1) was synthesized by the self-assembly of a ligand 2,5-thiophenediformates, 3,5-dimethylpyrazole and copper(II), and characterized by elemental analysis, IR and single-crystal X-ray diffraction. 1 crystallizes in monoclinic, space group C2/c with unit cell parameters, a=18.6156(4), b=5.96110(10), c= 18.1598(4)Å, =115.467(2)°, Z=4, V=1819.37(7)Å3, Mr = 425.94, Dc = 1.555g/cm3, μ=1.345mm-1, and F(000)= 876. The final R and wR are 0.0328 and 0.0816 for 7611 observed reflections with I>2σ(I). 1 shows an infinite 1-D polymeric chain structure based on the repeated basic units Cu(II)(3,5-dimethylpyrazole)2(2,5-thiophene diformate). The Cu(II)center acts as the joint of the unit, and is coordinated in a slightly distorted octahedral geometry comprised of four O atoms from two different 2,5-thiophenediformate ligands and two N atoms of two trans 3,5-dimethylpyrazole ligands.


1999 ◽  
Vol 52 (4) ◽  
pp. 271 ◽  
Author(s):  
Raymond C. Bott ◽  
Graham A. Bowmaker ◽  
Robbie W. Buckley ◽  
Peter C. Healy ◽  
M. C. Senake Perera

Two-coordinate gold(I) complexes, [Au(PCy3)X] (PCy3 = tricyclohexylphosphine, X = Cl, Br and I), have been prepared by reaction of stoichiometric quantities of [NBu4] [AuX2] and PCy3 in dimethylformamide and, for X = Cl and Br, by anodic dissolution of metallic gold in a solution of aqueous HX and PCy3 in acetonitrile. The complexes were characterized by solution and solid-state 31 P n.m.r. spectroscopy, far-infrared spectroscopy and single-crystal X-ray structure determinations. The chloride, bromide and iodide complexes form an isomorphous series, crystallizing in the triclinic space group P 1- (a ≈ 9·3, b ≈ 10·3, c ≈ 10·9 Å, α ≈ 88, β ≈ 80, γ ≈ 77°) as discrete molecules which stack in parallel head-to-tail mode to form a zigzag chain of gold atoms along the crystallographic c axis. Au ··· Au separations are 5·71, 6·20 Å for X = Cl, 5·72, 6·17 Å for X = Br and 5·74, 6·20 Å for X = I. The iodide also crystallizes as an orthorhombic form in space group Pnma (a 16·809(4), b 14·373(5), c 8·623(3) Å) with a different conformational structure for the PCy3 ligand and loss of the zigzag chain structure. Far-infrared spectra of the complexes show ν(AuX) at 332, 324 cm-1 for X = Cl and 232 cm-1 for X = Br with multiple bands in the region 150−200 cm-1 for both iodide complexes, precluding definitive assignment of ν(AuI). Solution 31 P n.m.r. spectra in chloroform give sharp single peaks with chemical shifts of 54·5, 56·6 and 59·9 ppm for X = Cl, Br and I respectively. The solid-state CPMAS 31 P n.m.r. spectra also yield single peaks with chemical shifts of 55 (Cl), 58 (Br) and 63 ppm (I) for the triclinic complexes and 57 ppm for the orthorhombic iodide. The chemical shift differences between the two forms of the iodide and between the complexes in the solution and solid states are ascribed to variations in the conformational structure of the phosphine ligands.


Sign in / Sign up

Export Citation Format

Share Document