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1.
The bright red title compound 1 was synthesized from (2-lithiophenyl)diphenylamine and bis(pentafluorophenyl)boron chloride. Its reactions with small acids like H 2O and HCl proceeded easily giving zwitterionic compounds. For 1 and its water adduct 2 the crystal structures were determined, the latter featuring an ammonium borate structure containing a short intramolecular hydrogen bond bridge. Treatment of 1 with Jutzi's acid, [H(OEt 2) 2][B(C 6F 5) 4], did not result in protonation of the nitrogen, but reaction of 1 with LiH in the presence of 12-crown-4, led to the isolation of the aminoborate [1-(Ph 2N)-2-{B(H)(C 6F 5) 2}C 6H 4][Li(12-crown-4)] (3). Borohydride 3 reacted with Jutzi's acid to regenerate 1 and liberate hydrogen. 相似文献
2.
The synthesis of a bulky secondary phosphine, Ar 2PH [Ar=C 6H 2(CF 3) 3-2,4,6], and its use in the first synthesis and isolation of a phosphonium phosphide, (Ph 3PMe)+(Ar 2P) −, via the deprotonation of Ar 2PH with a nonstabilised phosphorus ylide, Ph 3P=CH 2, are reported. An X-ray structure of this salt reveals that cations and anions are weakly associated in the solid state through C–HP interactions. 相似文献
3.
The solid-state structures of two non-metal pentaborates [Me 3NCH 2CH 2OH][B 5O 6(OH) 4] ( 1) and [4-MepyH, 4-Mepy][B 5O 6(OH) 4] ( 2) have been determined by single-crystal X-ray diffraction methods. Structures 1 and 2 both contain supramolecular pentaborate frameworks held together by extensive H-bond interactions. The framework of 1 exists essentially as planes of pentaborate anions linked via three pairwise ‘planar’ β → α interactions, with a fourth β → β interaction crosslinking the planes. The framework of 2 is very similar except that one of the three pairwise linkages within the plane is replaced by pairwise ‘step-like’ bifurcated H-bonds to both α sites of a neighboring anion. The cations in 1 and the cations and neutral 4-Mepy ligands in 2 are present in the framework cavities and channels, with additional H-bond interactions existing between cations and anions. 相似文献
4.
The reactions of [Fe 3(CO) 12] or [Ru 3(CO) 12] with RNC (R=Ph, C 6H 4OMe- p or CH 2SO 2C 6H 4Me- p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe 3(CO) 12], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe 3(CO) 10(CNPh) 2] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru 3(CO) 12] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru 4(CO) 11(CNPh) 3] was structurally characterised and has a spiked-triangular Ru 4 core with two of the CNPh ligands coordinated in an unusual μ 3-η 2 mode. 相似文献
5.
The reactions of [RuHCl(CO)(PPh 3) 3] and [(C 6H 6)RuCl 2] 2 with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh 3) 2(C 5H 4NCOO)] and [RuCl 2(C 12H 9NO) 2] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis. 相似文献
6.
The 31P chemical shift of the (C 6H 5) 3-nPX n ligands (X = Cl, Br, I; n = 0–3) is dominated by the electronegativity of the substituents. π bonding is only important for derivatives with three strongly electronegative substituents. The 31P chemical shift of the corresponding complexes (C 6H 5) 3-nPX nCr(CO) 5 is governed by the simultaneous effects of the electronegativity, steric hindrance and π bonding. The resonance parameter, δ', indicates an increasing ( pring → dp)π and ( dcr→ dp)π electron delocalization with halogen substitution. 相似文献
7.
The crystals of [C 9H 7NC 3H 5]Cu(SCN) 2 ( I) and [C 9H 7NC 3H 5]Cu 2(SCN) 3 ( II) were obtained in the reaction of N-allylquinolinium bromide with CuSCN and NH 4SCN in a methanol solution. The crystals of I are triclinic: space group P
, Z = 2, a = 8.619(2), b = 8.755(2), c = 10.463(3) ?, α = 77.18(3), β = 69.95(3), γ = 79.38(3)°, V = 718.1(3) ? 3. The crystals of II are opthorhombic: space group P2 12 12 1, Z = 4, a = 5.744(2), b = 16.799(4), c = 17.980(5), V = 1735.9(9) ? 3. The structure of compound I is built of infinite linear {Cu(SCN) 2−} ∞ anions and the N-allylquinolinium cations bonded additionally by relatively weak hydrogen contacts C-H...S. The [C 9H 7NC 3H 5] + cations are located between the corrugated layers of the {Cu 2(SCN) 3−} ∞ anions in compound II. As in the case of the previously studied copper(I) halide complexes, the C=C bond of the allyl group
in the N-allylquinolinium cation of complexes I, II does not interact with Cu(I).
Original Russian Text ? A.V. Pavlyuk, V. Kinzhybalo, T. Lis, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008,
Vol. 34, No. 10, pp. 764–769. 相似文献
8.
Diorganodiselenide [2-(Et 2NCH 2)C 6H 4] 2Se 2 ( 1) was obtained by hydrolysis/oxidation of the corresponding [2-(Et 2NCH 2)C 6H 4]SeLi derivative. The treatment of [2-(Et 2NCH 2)C 6H 4] 2Se 2 with elemental sodium in THF resulted in [2-(Et 2NCH 2)C 6H 4]SeNa ( 2). Reactions between alkali metal selenolates [2-(R 2NCH 2)C 6H 4]SeM′ (R = Me, Et; M′ = Li, Na) and MCl 2 (M = Zn, Cd) in a 2:1 molar ratio resulted in the [2-(R 2NCH 2)C 6H 4Se] 2M species [R = Me, M = Zn ( 3), Cd ( 4); R = Et, M = Zn ( 5), Cd ( 6)]. The new compounds were characterized by multinuclear NMR ( 1H, 13C, 77Se, 113Cd) and mass spectrometry. The crystal and molecular structures of 1, 3 and 4 revealed monomeric species stabilized by N → Se (for 1) and N → M (for 3 and 4) intramolecular interactions. 相似文献
9.
The reaction of [(C 6H 6)RuCl 2] 2 with 7,8-benzoquinoline and 8-hydroxyquinoline in methanol were performed. The obtained complexes have been studied by IR, UV–VIS, 1H and 13C NMR spectroscopy and X-ray crystallography. In the reaction with 8-hydroxyquinoline the arene ruthenium(II) complex oxidized to Ru(III). The electronic spectra of the obtained compounds have been calculated using the TDDFT method. Magnetic properties of [Ru(C 9H 6NO) 3] · CH 3OH complex suggest the antiferromagnetic coupling of the ruthenium centers in the crystal lattice. EPR spectrum of [Ru(C 9H 6NO) 3] · CH 3OH compound indicates single isotropic line only characteristic for Ru 3+ with spin equal to 1/2. 相似文献
11.
The title compound ( 1) was prepared by the reaction of 3,5-bis(CF 3)C 6H 3P( i-C 3H 7) 2 ( L1) and Co 2(CO) 8. Its solubility in supercritical carbon dioxide was measured at varying temperatures and pressures using a modified analytical extraction device. Solubility data were determined in the temperature and pressure ranges between 40 and 70 °C and between 100 and 300 bar, respectively. The solubility of 1 is lower compared to ( p-CF 3C 6H 4) 3P, but much higher than for transition metal complexes bearing phosphines without fluorinated substituents. 相似文献
12.
The chemistry of η 3-allyl palladium complexes of the diphosphazane ligands, X 2PN(Me)PX 2 [X = OC 6H 5 ( 1) or OC 6H 3Me 2-2,6 ( 2)] has been investigated.The reactions of the phenoxy derivative, (PhO) 2PN(Me)P(OPh) 2 with [Pd(η 3-1,3-R′,R″-C 3H 3)(μ-Cl)] 2 (R′ = R″ = H or Me; R′ = H, R″ = Me) give exclusively the palladium dimer, [Pd 2{μ-(PhO) 2PN(Me)P(OPh) 2} 2Cl 2] ( 3); however, the analogous reaction with [Pd(η 3-1,3-R′,R″-C 3H 3)(μ-Cl)] 2 (R′ = R″ = Ph) gives the palladium dimer and the allyl palladium complex [Pd(η 3-1,3-R′,R″-C 3H 3)( 1)](PF 6) (R′ = R″ = Ph) ( 4). On the other hand, the 2,6-dimethylphenoxy substituted derivative 2 reacts with (allyl) palladium chloro dimers to give stable allyl palladium complexes, [Pd(η 3-1,3-R′,R″-C 3H 3)( 2)](PF 6) [R′ = R″ = H ( 5), Me ( 7) or Ph ( 8); R′ = H, R″ = Me ( 6)].Detailed NMR studies reveal that the complexes 6 and 7 exist as a mixture of isomers in solution; the relatively less favourable isomer, anti-[Pd(η 3-1-Me-C 3H 4)( 2)](PF 6) ( 6b) and syn/ anti-[Pd(η 3-1,3-Me 2-C 3H 3)( 2)](PF 6) ( 7b) are present to the extent of 25% and 40%, respectively. This result can be explained on the basis of the steric congestion around the donor phosphorus atoms in 2. The structures of four complexes ( 4, 5, 7a and 8) have been determined by X-ray crystallography; only one isomer is observed in the solid state in each case. 相似文献
13.
The reaction of the anion [( tBuP) 3As] − ( 1) with Me 2SiCl 2 results in nucleophilic substitution of the Cl − anions, giving the di- and mono-substituted products [Me 2Si{As(P tBu) 3} 2] ( 3a) and [Me 2Si(Cl){As(P tBu) 3}] ( 3b). Analogous reactions of the pre-isolated [(CyP) 4As] − anion ( 2) (Cy = cyclohexyl) with Me 2SiCl 2 produced mixtures of products, from which no pure materials could be isolated. However, reaction of 2 [generated in situ from CyPHLi and As(NMe 2) 3] gives the heterocycle [(CyP) 3SiMe 2] ( 4). The X-ray structures of 3a and 4 are reported. 相似文献
14.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
15.
Abstract The 18-metallacrown-6 metallamacrocycle [Fe 6(pmshz) 6(C 4H 9NO) 6] has been synthesized by the self-assembly reaction of iron ions with N-substituted salicylhydrazide ligands. Six Fe(III) ions and six deprotonated N-propanoyl-4-methylsalicylhydrazide (H 3 pmshz) ligands construct a planar 18-membered ring based on Fe–N–N–Fe linkage. Because of the coordination, the ligand enforces
the stereochemistry of the Fe(III) ions as a propeller shape with alternating …ΔΛΔΛ… configurations. There is a strong antiferromagnetic
exchange interaction between the paramagnetic iron centers. 相似文献
16.
Chiral “P-N-P” ligands, (C 20H 12O 2)PN(R)PY 2 [R = CHMe 2, Y = C 6H 5 ( 1), OC 6H 5 ( 2), OC 6H 4-4-Me ( 3), OC 6H 4-4-OMe ( 4) or OC 6H 4-4- tBu ( 5)] bearing the axially chiral 1,1′-binaphthyl-2,2′-dioxy moiety have been synthesised. Palladium allyl chemistry of two of these chiral ligands ( 1 and 2) has been investigated. The structures of isomeric η 3-allyl palladium complexes, (R′ = Me or Ph; Y = C 6H 5 or OC 6H 5) have been elucidated by high field two-dimensional NMR spectroscopy. The solid state structure of [Pd(η 3-1,3-Ph 2-C 3H 3){κ 2-( racemic)-(C 20H 12O 2)PN(CHMe 2)PPh 2}](PF 6) has been determined by X-ray crystallography. Preliminary investigations show that the diphosphazanes, 1 and 2 function as efficient auxiliary ligands for catalytic allylic alkylation but give rise to only moderate levels of enantiomeric excess. 相似文献
17.
Treatment of p- tert-butylcalix[4]areneH 4 iwth AlMe 3 in toluene at elevated temperature affords after work-up the complex {[MeAl(NCMe)] 2( p- tert-butylcalix[4]arene)}, which adopts a flattened partial cone conformation as characterized by X-ray crystallographu. 相似文献
18.
Crystal structure of 1-dodecylamine hydrochloride (C 12H 28NCl)(s) has been determined by an X-ray crystallography. Lattice potential energy and the molar volumes of the solid compound and its cation were respectively obtained. The enthalpy of dissolution of the compound was measured by an isoperibol solution-reaction calorimeter at 298.15 K. The molar enthalpy of dissolution at infinite dilution was determined to be , and relative apparent molar enthalpies ( ΦL), relative partial molar enthalpies ( L2) of the compound and relative partial molar enthalpies ( L1) of the solvent (double distilled water) at different concentrations m (mol kg −1) were obtained through fitted multiple regression equation by means of Pitzer's theory. Finally, hydration enthalpies of the substance and its cation were calculated by designing a thermochemical cycle in accordance with lattice potential energy and the molar enthalpy of dissolution at infinite dilution . 相似文献
19.
We report a new synthesis and characterization of Ir(C 2H 4) 2(C 5H 7O 2) [(acetylacetonato)-bis(η 2-ethene)iridium(I)], prepared from (NH 4) 3IrCl 6 · H 2O in a yield of about 45%. The compound has been characterized by X-ray diffraction crystallography, infrared, Raman, and NMR spectroscopies and calculations at the level of density functional theory. Ir(C 2H 4) 2(C 5H 7O 2) is isostructural with Rh(C 2H 4) 2(C 5H 7O 2), but there is a substantial difference in the ethylene binding energies, with Ir-ethylene having a stronger interaction than Rh-ethylene; two ethylenes are bound to Ir with a binding energy of 94 kcal/mol and to Rh with a binding energy of 70 kcal/mol. 相似文献
20.
A novel bisphosphine ligated Ag 60 nanocluster, [{Cl@Ag 12}@Ag 48(dppm) 12], has been dis-covered and characterized by X-ray crystallography. It consists of a central chloride located inside an icosahedral silver core layer, which is further encased by a second shell of 48 silver atoms/ions, which are capped with 12 bis(diphenylphosphino)methane (dppm) ligands. Due to lack of sufficient material the cluster could not be further characterized by other methods. DFT calculations were carried out on the cation [{Cl@Ag 12}@Ag 48(dppm) 12] + to determine if it corresponds to a superatom with a core count of n=58. The DFT optimized structure is in agreement with X-ray ndings, but the low value of the HOMO-LUMO gap does not support superatom stability. 相似文献
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