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1.
Chemical vapor deposition experiments were conducted using phosphinoborane compounds of the type [R2BPR′2]n, where R = CH2CH3 (1) or CH3 (2), R′= C(CH3)3, and R = CH2CH3 (3) or CH3 (4), R′ = Si(CH3)3. Thin films were deposited on Si substrates at 300–850°C under vacuum using 1–3, while no film formed using 4. All films contained considerable carbon (C/B = 0.67–7) and were deficient in phosphorus (P/B = 0-0.5) according to Auger electron spectroscopy. For 3, silicon was incorporated in the films (Si/B = 0.9–2). The preferential loss of phosphorus was nearly complete at higher pyrolysis temperatures that favor formation of carbon-rich films. Volatile products of the decompositions were observed by in situ mass spectroscopy and by 1H nuclear magnetic resonance analysis of the condensate in a liquid nitrogen cooled trap. The products indicate that β-hydrogen elimination of alkene from boron is a preferred reaction pathway, while concerted elimination reactions appear to be inefficient. Although these phosphinoborane compounds do not appear to be suitable precursors for pure boron phosphide, the B-P-C films obtained are chemically inert and may be of interest as protective coatings. 相似文献
2.
Ekkehard Lindner Ulf Kehrer Manfred Steimann Markus Strbele 《Journal of organometallic chemistry》2001,630(2):3021-274
A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH2O(CH2CH2O)nCH2CH2PPh2)2]PtCl2 (n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH2O(CH2CH2O)nCH2CH2PPh2)2 (n=1–3) (3a–c) and (PhCN)2PtCl2 under high dilution conditions in CH2Cl2. The bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1′-Fc(CH2O(CH2CH2O)nCH2CH2OH)2 (n=1–3) (1a–c) with: (i) CH3SO2Cl in CH2Cl2 and (ii) LiPPh2 in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg2+, or NH4+ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest complexes for 4a,b. In the case of 4c only the addition of Na+ or K+ leads to an insignificant effect. 相似文献
3.
Felix D. Sokolov Damir A. Safin Nail G. Zabirov Alexander Yu. Verat Vasiliy V. Brusko Dmitry B. Krivolapov Ekaterina V. Mironova Igor A. Litvinov 《Polyhedron》2006,25(18):3611-3616
The reaction of bis-thiourea o-C6H4[NHC(S)NHP(S)(Oi-Pr)2]2 (1) with iodine, KOH and ClCH2C(O)OCH3 leads to O,O′-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylideneamidothiophosphate (2) formation. The complex of the potassium salt of compound 2 with 18-crown-6, having the composition [K(18-crown-6)L], has been synthesized. Bis-thiourea [CH2NHC(S)NHP(S)(Oi-Pr)2]2 (6) forms a stable potassium salt, which oxidation by iodine leads to a product of heterocyclization, O,O′-diisopropyl-(1-{[(diisopropoxyphosphorothio)amino]carbonothioyl}imidazolidine-2-ylidene)amidothiophosphate (8), in which one of the thiourea fragments is kept. 相似文献
4.
Takeshi Sakaizumi Hirotaka Imajo Ryo Sekiya Nobuhiko Kuze Osamu Ohashi 《Journal of Analytical and Applied Pyrolysis》2001,60(2):131-144
The pyrolysis products of CH2=C(CH3)---NO (syn form) have been determined by microwave spectroscopy. The pyrolysis products of CH2=C(CH3)---NO (syn form) and its 15N isotopic species were found to be CH2=O, CH3CN, and CH3C15N. The produce of formaldehyde and methyl cyanide suggests that the C=C and N=O double bonds of CH2=C(CH3)---N=O (syn form) were broken. To explain the generation of the two molecules, a four-membered ring molecule (9) as an intermediate, is proposed. The four-membered ring molecule as an intermediate is also supported by ab initio MO calculation. Applying the pyrolysis mechanism obtained for 2-nitrosopropene (syn form) to that of 1,1,2-trichloronitrosoethane, one of its complicated pyrolysis mechanisms was explained. The rotational constants and geometrical parameters of two intermediates, 9 and CH2=CCl---NO (13), were obtained by ab initio MO calculation (MP2/6-31G**) to predict their microwave spectra. 相似文献
5.
William Henderson Brian K. Nicholson Allen G. Oliver 《Journal of organometallic chemistry》2001,620(1-2):182-189
The reactions of the cyclo-aurated gold(III) dihalide complex [{C6H3(CH2NMe2)-2-(OMe)-5}AuCl2] with N-cyanoacetylurethane [NCCH2C(O)NHCO2Et], 2-benzoylacetanilide [PhC(O)CH2C(O)NHPh] and acetoacetanilide [MeC(O)CH2C(O)NHPh], and [{C6H4(CH2NMe2)-2}AuCl2] with acetoacetanilide in dichloromethane with excess silver(I) oxide gives the first examples of auralactam complexes, containing
(O)---CHR′ four-membered rings. A single-crystal X-ray diffraction study on the complex [{C6H4(CH2NMe2)-2}A
H(COMe)}] reveals similar structural features to related metallalactam complexes of platinum(II) and palladium(II). When a CDCl3 solution of the complex [{C6H3(CH2NMe2)-2-(OMe)-5}A
HCN}] is allowed to stand for 18 h, a novel dimerisation reaction occurs, giving the insoluble product [{C6H3(CH2NMe2)-2-(OMe)-5}Au{N(CO2Et)C(O)CHCN}]2·2CDCl3, characterised by an X-ray structure determination. The dimer contains an eight-membered A ring. 相似文献
6.
The results of ab initio calculations at the MP2/6-31G(d) level of molecules of the series ClPXX′ (X, X′=C2H5, N(CH3)2, OCH3) and ClP(M)XX′ (M=O, S; X=CH3, ?CH3; X′=C2H5, OCH3) with total optimization of their geometry were presented. They were compared with the obtained earlier results of such calculations at the RHF/6-31G(d) level and with experimental 35Cl nuclear quadrupole resonance (NQR) spectra for these compounds. MP2/6-31G(d) calculations confirm non-inductive influence of heteroatoms on the geminal Cl atom in the non-linear three-atomic Cl–P–M groups. They agree to the conclusion that the abnormal correlation of the 35Cl NQR frequencies for the compounds studied at different X, X′ and M is caused, in general, by the P–Cl bond polarization under the action of the geminal atom partial charges directly through the field. The satisfactory conformity between the experimental 35Cl NQR frequencies and those estimated from 3p-components of the Cl atom valence p-orbitals calculated at the MP2/6-31G(d) level was obtained. 相似文献
7.
L. A. Errede 《Advances in colloid and interface science》1995,60(3):119-198
The adsorption parameters () for five branched aliphatic ethers were established experimentally in the usual way [17]. It was shown that when this set of -values is combined with the set already established for the unbranched ethers [17], the union set enables one to estimate with reasonable confidence the -values for all the possible structural permutations derivable from the general molecular structure [GMS] H(CH2)m+1[(CH3)q′CH2−q′ OCH2−q(CH3)q](CH2)n+1H, and for a portion of those that are derivable from the GMS (CH3)q′+1CH2−q′[(CH2)mO(CH2)n]CH2−q(CH3)q+1, using the corresponding Log vs N linear relationship deduced in these and earlier sorption studies, in which N = m+n+q+q′+4. It was shown that the data for the -values derived thereby comprise a self-consistent rigidly interconnected multidimensional universe of linear Log vs N relationships that represent series of subsets of the above GMSs resulting from varying one integer (m+n+q or ′) while the other three are held constant. 相似文献
8.
Donald C. Bradley Michael B. Hursthouse Ali A. Ibrahim K. M. Abdul Malik Majid Motevalli Reinhold M seler Harold Powell John D. Runnacles Alice C. Sullivan 《Polyhedron》1990,9(24):2959-2964
Transamination reactions utilizing the compound mercuric bis(trimethylsilyl)amide, Hg{N(SiMe3)2}2, in tetrahydrofuran (THF), and the metals Na, Mg, Ca, Sr, Ba and Al have been investigated. Thus the THF solvated compounds Na[N(SiMe3)2]·THF and M[N(SiMe3)2]2·2THF, M = Mg, Ca, Sr and Ba (1–4), have been prepared. The X-ray crystal structures of 1 and the related manganese compound Mn[N(SiMe3)2]2·2THF (5) are reported. Interaction of the silylamides, 2–4, with a range of crown ethers apparently proceeded with elimination of silylamine, (Me3Si)2NH, and novel ring opening of the crown ethers, generating species containing a donor alkoxide ligand with a vinyl ether function, presumably, ---O(CH2CH2O)nCH=CH2 (n = 3−5). The silylamides 2–4 were also cleanly converted to the corresponding alkoxides (from 1H NMR data) in reactions with stoichiometric quantities of 3-ethyl-3-pentanol. 相似文献
9.
New ester salts [R3NH]+[F5SC(SO2F)C(O)OR′]− where RH, CH3CH2 and R′CH3,(CH3)2CH have been prepared from corresponding esters and amines. The sodiumsalt Na[F5SC(SO2F)C(O)OCH(CH3)2] was used to prepare the following -substitutedderivatives: SF5CX(SO2F)C(O)OCH(CH3)2, XBr, Cl. The crystal structure of[(C2H5)3NH]+[F5SC(SO2F)C(O)OCH3]− was determined and is monoclinic: P21/n;a=8.758(2) Å, b=9.645(2) Å and c=19.167(4) Å; β=97.92(3)°; V=1603.6 Å3; Z=4. 相似文献
10.
The Schiff base compound, N-N′-bis(4-methoxybenzylidene)ethylenediamine (C18H20N2O2) has been synthesized and its crystal structure has been investigated by X-ray analysis and PM3 method. The compound crystallizes in monoclinic space group P21/n with a=10.190(1), b=7.954(1), c=10.636(1) Å, β=111.68(1)°, V=801.1(1) Å3, Z=2 and Dcal=1.229 Mgm−3. The title structure was solved by direct methods and refined to R=0.056 for 2414 reflections [I>3.0σ(I)] by full-matrix anisotropic least-squares methods. The energy profile of the compound was calculated by PM3 method as a function of θ[N1′–C9′–C9–N1]. The most stable molecular structure of the title compound is the anti conformation, which is different in energy by 5.0 and 1.0 kcal mol−1 from the eclipsed conformation I and gauche conformations, (III and V), respectively. 相似文献
11.
A. Elmali M. Kabak E. Kavlakoglu Y. Elerman T. N. Durlu 《Journal of Molecular Structure》1999,510(1-3):207-214
The crystal structure of N-(2-hydroxy-5-chlorophenyl) salicylaldimine (C13H10NO2Cl) was determined by X-ray analysis. It crystallizes orthorhombic space group P212121 with a=12.967(2) Å, b=14.438(3) Å, c=6.231(3) Å, V=1166.5(6) Å3, Z=4, Dc=1.41 g cm−3 and μ(MoK)=0.315 mm−1. The title compound is thermochromic and the molecule is nearly planar. Both tautomeric forms (keto and enol forms in 68(3) and 32(3)%, respectively) are present in the solid state. The molecules contain strong intramolecular hydrogen bonds, N1–H1O1/O2 (2.515(1) and 2.581(2) Å) for the keto form and O1–H01N1 for the enol one. There is also strong intermolecular O2–HO1 hydrogen bonding (2.599(2) Å) between neighbouring molecules. Minimum energy conformations AM1 were calculated as a function of the three torsion angles, θ1(N1–C7–C6–C5), θ2(C8–N1–C7–C6) and θ3(C9–C8–N1–C7), varied every 10°. Although the molecule is nearly planar, the AM1 optimized geometry of the title compound is not planar. The non-planar conformation of the title compound corresponding to the optimized X-ray structure is the most stable conformation in all calculations. 相似文献
12.
《Polyhedron》1988,7(24):2601-2603
Distibines of the type R2SbSbR′2 with R = CH3, R′ = C2H5 (1), R = CH3, R′= n-C3H7 (2), R = CH3, R′= C6H5 (3), R = C2H5, R′= C6H5 (4), R = n-C3H7, R′ = C6H5 (5), and R = CH3, R′ = 2,4,6-(CH3)2C6H2 (6) are formed in equilibria by exchange reactions of the respective distibines of the type R4Sb2 and R′4Sb2. 相似文献
13.
Treatment of p-tert-butylcalix[6]areneH6 (H6L) with [Mo(OBut)2{[2,2′-(N)-C6H4]2(CH2CH2)}] in refluxing toluene affords, after work-up, the complex [Mo(2-NC6H4CH2CH2C6H4NHC(Me)NH-2/)LH2]·4MeCN (1), which contains an 11-membered metallocyclic ring as characterised by Synchrotron X-radiation. 相似文献
14.
In order to gain information about the coordinating properties of the chelating ligands Me2XGeMe2(CH2)2X′Me2 (abbr. XGeCCX′) the chemical and spectroscopic results obtained during the synthesis of the M(CO)4(XGeCCX′) complexes (M = Cr, Mo, W; X, X′ = N, P, As) are critically discussed and compared with the results for the analogous five-membered ring chelates M(CO)4(KGeCX′). 相似文献
15.
The photophysical properties, which vary as R is varied, of a series of [Pt(N2O2)] complexes bearing bis(phenoxy)bipyridine auxiliaries with different substituents R=H (Pt-H) (1), 4,4′-2NH2 (Pt-NH2) (2), 4,4′-2tBu (Pt-tBu) (3), 4,4′-2CN (Pt-CN) (4), and 4,4′-2NO2 (Pt-NO2) (5) are investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The solvent effects are discussed in CH2Cl2, CH3CN and CH3OH solutions, respectively, by polarizable continuum model (PCM). It is anticipated that compared with σ-donor substituents, π-acceptors have more dramatic effects on the electronic and optical properties in this series of complexes. Introduction of π-electron withdrawing substituents on bipyridine ligand will benefit the LLCT (or MLCT) and prohibit the non-radiative pathways via d–d transitions by increasing the energy gap between the HOMO–LUMO and d–d transitions. The results also reveal that the lowest-energy excitations of all complexes show blue-shifts in the polarized solution and when the polarity of the solvent increases from CH2Cl2, CH3CN and CH3OH, the low-energy broad absorption band exhibit blue-shifts. The lowest-energy excitations and photoluminescence of all complexes are dominated by π(phenoxy)→π*(bpy/NO2) (LLCT) excited state mixed with some energetically dπ (Pt)→π*(bpy/NO2) (MLCT) transition. 相似文献
16.
Taku Katayama Kiyotaka Onitsuka Shigetoshi Takahashi 《Journal of organometallic chemistry》2000,610(1-2):31-37
Treatment of ruthenium complexes [CpRu(AN)3][PF6] (1a) (AN=acetonitrile) with iron complexes CpFe(CO)2X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I) in refluxing CH2Cl2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)2X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN)2][PF6] (1b: L=CO, 1c: P(OMe)3) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH2Cl2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe3. 相似文献
17.
The electronic structure of N-sulfonylimines has been studied in detail using ab initio MO and density functional methods. The S–N rotational barriers in HS(O)2N=CH2 at G2MP2 and CBS-Q levels have been found to be 3.25 and 3.43 kcal/mol respectively. Complete optimization at HF/6-31+G*, MP2(full)/6-31+G* and B3LYP/6-31+G* levels have shown that synperiplanar arrangement of S–O with respect to C=N is more stable. NBO analysis has been carried out to quantitatively estimate these delocalisations and charge polarization in RS(O)2N=CH2 (R=H, Me, Cl, F). The Lewis basic character in N-sulfonylimines is less compared to N-alkylimines due to anomeric interactions that reduce the lone pair electron density on nitrogen in 1. 相似文献
18.
The vapour pressuresof liquid cyclohexane + N, N, N′, N′-tetramethylalkanediamine, (CH3)2 N(CH2)uN(CH3)2 (u = 1,2) + cyclohexane mixtures were measured by a static method between 303.15 and 343.15 K at 10 K intervals. The excess molar enthalpies at 303.15 K were also measured.
The molar excess Gibbs energies, calculated from the vapour-liquid equilibrium data, and the molar excess enthalpies compare satisfactorily with group contribution (DISQUAC) predictions.
The proximity effect of N atoms produces a regular decrease of the interactional parameters. 相似文献
19.
20.
Judith Bravo Carlos Cativiela Rafael Navarro Esteban P. Urriolabeitia 《Journal of organometallic chemistry》2002,650(1-2):157-172
The chiral bis-imine (1R,2R)-C6H10-[E---N=CH---C6H3---3,4-(OMe)2]2 1 (LH) reacts with [Pd(OAc)2] (1:1 molar ratio; OAc=acetate) giving the orthometallated [Pd(OAc)(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)-C6H10---N=CH---C6H3-3′,4′-(OMe)2-κ-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-κ-C,N,N)]), through C---H bond activation on only one of the aryl rings and N,N-coordination of the two iminic N atoms. 2 reacts with an excess of LiCl to give [Pd(Cl)(L-κ-C,N,N)] 3. The reaction of 3 with AgClO4 and neutral or anionic ligands L′ (1:1:1 molar ratio) affords [Pd(L-κ-C,N,N)(L′)](ClO4) (L′=PPh3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(I)(L-κ-C,N,N)] 8. Complex 4a reacts with wet CDCl3 giving [Pd(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)---C6H10---NH2-κ-C,N,N)(PPh3)](ClO4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b·CH2Cl2 has been determined by X-ray diffraction methods. Cleavage of the Pd---N bond trans to the Caryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac-O,O′)(L-κ-C,N)] 9 and [Pd(L-κ-C,N)(dppe-P,P′)](ClO4) 12, while classical N,N′-chelating ligands such as 1,10-phenantroline (phen) or 2,2′-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-κ-C,N,N)(κ1-N-phen)](ClO4) 10 and [Pd(L-κ-C,N,N)(κ1-N-bipy)](ClO4) 11. Treatment of 1 with PtCl2(DMSO)2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl2Pt[(NH2)2C6H10---N,N′] 13a and [Pt(Cl)(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)---C6H10---NH2-κ-C,N,N)] 13b, while [Pt(Cl)(L-κ-C,N,N)] 14 can be obtained by reaction of [Pt(μ-Cl)(η3-2-Me---C3H4)]2 with 1 in refluxing CHCl3. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity. 相似文献