Search results for "Bond length"
showing 10 items of 209 documents
Cyclometallation reactions in complexes of the type Rh(oq)(CO)(P(o-BrC6F4)Ph2)
1986
Abstract The reaction of Rh(oq)(CO)(PCBr) (PCBr = P(o-BrC6F4)Ph2; oq = 8-oxyquinolinte)_ in refluxing toluene in the presence of Et4NBr (1/4 molar ratio) gives Rh(oq)Br(PC) (H2O), PC = P (o-C6F4)Ph2, in practically quantitative yield. The water molecule is readily displaced by various P-donor ligands to give complexes of general formula Rh(oq)Br(PC) PR3 (PR3 = PPh3, P(p-MeC6H4)3, P(p-MeOC6H4)3, P(p-FC6H4)3, P(PMe)3 and P(OPh3). The molecular structure of the compound Rh(oq)Br(PC) (PPh3) has been determined by X-ray methods. Crystals of the title compound are monoclinic, space group P21/n with unit cell dimensions a 11.273(4), b 20.087(8), c 17.471(7) A and β 102.15(8)°. The final R for 2304…
Superoxide dismutase activity of ternary copper complexes of sulfathiazole and imidazole derivatives. Synthesis and properties of [CuL2(R-Him)2] [HL=…
2000
Abstract New ternary copper(II) complexes of sulfathiazole (4-amino-N-(thiazol-2-yl)benzenesulfonamide)(HL) and methyl imidazole derivatives have been synthesised and characterised. The crystal structure of the complex [CuL2(4,4-dmHim)2] (1) [4,4-dmHim=4,4-dimethylimidazoline] has been determined. The copper centre has a quasi regular square planar environment with Cu-nitrogen bond lengths ranging from 1.952 to 2.010 A. From the spectroscopic properties of the complexes [CuL2(1,2-dmHim)2] (2) [1,2-dmHim=1,2-dimethylimidazole] and [CuL2(4-mHim)2] (3) [4-mHim=4-methylimidazole] a distorted tetragonal octahedral geometry is deduced. The compounds showed SOD mimetic activity in fact, a low conc…
Crystal structures and magnetic properties of uniform and alternating azido-bridged (2,2′-bipyridyl)copper(II) chains
1998
Abstract Single crystals of four copper(II) complexes of formula [Cu(bipy)(N3)2]n (1,2), [Cu(bipy)2(N3)(ClO4)] (3) and [Cubipy)2(N3)]ClO4 (4) (bipy=2,2′-bipyridine) were obtained from aqueous solutions containing (2,2′-bipyridyl) copper(II) perchlorate and sodium azide, and their crystal structures were determined by X-ray diffraction methods. The structures of compounds 1 and 4 were already known, but the better accuracy of our structural determination of complex 1 led us to reconsider it here. The structures of compounds 1 and 2 are made up of neutral chains of copper(II) ions bridged by two azide groups exhibiting asymmetrical end-on (1) and alternating asymmetrical end-on and end-to-end…
Generation, Characterization, and Electrochemical Behavior of the Palladium-Hydride Cluster [Pd3(dppm)3(3-CO)(3-H)]+ (dppm=Bis(diphenylphosphinometha…
2007
Addition of formate on the dicationic cluster [Pd(3)(dppm)(3)(mu(3)-CO)](2+) (dppm=bis(diphenylphosphinomethane) affords quantitatively the hydride cluster [Pd(3)(dppm)(3)(mu(3)-CO)(mu(3)-H)](+). This new palladium-hydride cluster has been characterised by (1)H NMR, (31)P NMR and UV/Vis spectroscopy and MALDI-TOF mass spectrometry. The unambiguous identification of the capping hydride was made from (2)H NMR spectroscopy by using DCO(2) (-) as starting material. The mechanism of the hydride complex formation was investigated by UV/Vis stopped-flow methods. The kinetic data are consistent with a two-step process involving: 1) host-guest interactions between HCO(2) (-) and [Pd(3)(dppm)(3)(mu(3…
Synthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]−: structural diversity in lithium(i), zinc(ii) and nickel(ii) complexes
2016
A high-yield synthesis of [Li{S(H)C(PPh2S)2}]2 [Li2·(3)2] was developed and this reagent was used in metathesis with ZnCl2 and NiCl2 to produce homoleptic complexes 4 and 5b in 85 and 93% yields, respectively. The solid-state structure of the octahedral complex [Zn{S(H)C(PPh2S)2}2] (4) reveals notable inequivalence between the Zn-S(C) and Zn-S(P) contacts (2.274(1) Å vs. 2.842(1) and 2.884(1) Å, respectively). Two structural isomers of the homoleptic complex [Ni{S(H)C(PPh2S)2}2] were isolated after prolonged crystallization processes. The octahedral green Ni(ii) isomer 5a exhibits the two monoprotonated ligands bonded in a tridentate (S,S',S'') mode to the Ni(ii) centre with three distinctl…
Crystal structure of ethyl 2-(di-eth-oxy-phosphor-yl)-2-(2,3,4-tri-meth-oxy-phen-yl)acetate.
2014
The title compound, C17H27O8P, was prepared by Michaelis–Arbuzov reaction of ethyl 2-bromo-2-(2,3,4-trimethoxyphenyl)acetate and triethyl phosphite. Such compounds rarely crystallize, but single crystals were recovered after the initial oil was left for approximately 10 years. The bond angle of thesp3-hybridized C atom connecting the benzene derivative with the phospho unit is widened marginally [112.5 (2)°]. The terminal P—O bond length of 1.464 (2) Å clearly indicates a double bond, whereas the two O atoms of the ethoxy groups connected to the phosphorous atom have bond lengths of 1.580 (2) Å and 1.581 (3) Å. The three methoxy groups emerge out of the benzene-ring plane due to steric hind…
G2(MP2) molecular orbital study of the substituent effect in the H3BPH3−nFn (n=0–3) donor–acceptor complexes
2000
Abstract The complexation energies of H3BPH3−nFn (n=0–3) and the proton affinities of PH3−nFn compounds have been investigated at the G2(MP2) level of theory. G2(MP2) results show that the successive fluorine substitution on the phosphine increases the stability of H3BPH3−nFn complexes although the basicity of the PH3−nFn ligands reduces with this substitution. The NBO partitioning scheme shows that this stability was related to the hyperconjugation effect. It proves also that the shortening of the P–H and P–F bond lengths, upon complexation, is due to an increasing `s' character in these bonds.
Study of the mutual influence of ligands in cobalt(II) complexes containing thiocyanate and imidazole derivatives
1997
Abstract The cobalt(II) complexes of formula [Co(NCS)2L2] and [Co(NCS)2L′4] (L = imidazole (iz) derivatives, I-Meiz (1), Z-Meiz (2), 2-Etiz (3), 2-Isopropiz (4), 2-Pheniz (5), 1,2-Me2iz (6), Biz (7), 2-Mebiz (8), 2-Etbiz (9); L′ = iz (10), 1-Meiz (11)) have been synthesized and characterized by spectroscopic methods and magnetic measurements. The crystal and molecular structures of complexes 6 and 11 have been determined by X-ray diffraction methods. Complex 6 crystallizes inthe orthorhombic space group Pnma with cell constants a=9.209 (3), b = 12.462 (5), c = 14.851(3) A ; V = 1704.3(9) A 3 , D ( calc ., Z = 4) = 1.43 g cm −3 , M r =367.35, F(000)=640 , λ( Mo K α)=0.71079 A , μ=11.2 cm−1 a…
Ferromagnetic Coupling Through the End-to-End Thiocyanate Bridge in Cobalt(II) and Nickel(II) Chains
2015
The preparation, spectroscopic characterization, and X-ray crystal structure of two novel one-dimensional compounds of formula [MII(tppz)(NCS)(μ-1,3-NCS)]n [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and M = Co(1) and Ni (2)] are reported. 1 and 2 are isomorphous compounds, and they crystallize in the P21/n space group. Their structures are made up of zigzag chains of cobalt(II) (1) and nickel(II) ions (2) bridged by single end-to-end thiocyanate groups with a tridentate tppz molecule and a terminally bound thiocyanate-N ligand achieving distorted MN5S octahedral surroundings around each metal center. The main source of the distortion of the ideal octahedron is due to the geometrical constr…
Orthometallation reactions of tris(p-methoxyphenyl)phosphine with dirhodium(II) tetraacetate
1998
Abstract Reactions of dirhodium(II)tetraacetate [Rh2(OAc)4] with tris(p-methoxyphenyl)phosphine (PMP) at 1:1 and 1:2 molar ratios yield, first appropriate adducts: [Rh2(OAc)4P(p-CH3OC6H4)3] (1a) and [Rh2(OAc)4{P(p-CH3OC6H4)3}2] (2a), and then orthometallated [Rh2(OAc)3{μ-(p-CH3OC6H3)P(p-CH3OC6H4)2}(HOAc)2] (1) and [Rh2(OAc)2{μ-(p-CH3OC6H3)P(p-CH3OC6H4)2}2(HOAc)2] (2) complexes, respectively. They have been characterized by spectroscopic methods. The molecular structure of 1 has been determined by the X-ray methods. Crystal data: space group P1, a=11.085(5), b=11.387(5), c=13.900(6) A, α=97.29(3), β=105.23(3), γ=91.93(3)°. In this compound The Rh–Rh distance is 2.421(1), Rh–P bond length 2.1…