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1.
A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph 3GeCHR 1CHR 2CO 2) nSbAr (5−n) (R 1=H, Ph; R 2=H, CH 3; n=1, 2) were synthesized and characterized by elemental analysis, IR, 1H-NMR, 13C-NMR and mass spectroscopy. The crystal structures of Ph 3GeCH(Ph)CH 2CO 2SbPh 4 and [Ph 3GeCH 2CH(CH 3)CO 2] 2Sb(4-ClC 6H 4) 3 were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported. 相似文献
2.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
3.
The interaction of [(η 5-C 5H 4Bu t) 2YbCl · LiCl] with one equivalent of Li[(CH 2) (CH 2)PPh 2] in tetrahydrofuran gave [Ph 2PMe 2][(η 5-C 5H 4Bu t) 2Li] (1) and [(η 5-C 5H 4Bu t) 2Yb(Cl)CH 2P(Me)Ph 2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph 2PMe 2][CF 3SO 3] with two equivalents of (C 5H 4Bu t)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η 5-C 5H 4Bu t) 2Li] − anion. 相似文献
4.
The reaction of Ln(NO 3) 3·6H 2O (Ln=La, Ce, Pr or Nd) with a sixfold excess of Ph 3PO in acetone formed [Ln(Ph 3PO) 4(NO 3) 3]·Me 2CO. The crystal structure of the La complex shows a nine-coordinate metal centre with four phosphine oxides, two bidentate and one monodentate nitrate groups, and PXRD studies show the same structure is present in the other three complexes. In CH 2Cl 2 or Me 2CO solutions, 31P NMR studies show that the complexes are essentially completely decomposed into [Ln(Ph 3PO) 3(NO 3) 3] and Ph 3PO. Similar reactions in ethanol gave [Ln(Ph 3PO) 3(NO 3) 3] only. In contrast for Ln=Sm, Eu or Gd, only the [Ln(Ph 3PO) 3(NO 3) 3] are formed from either acetone or ethanol solutions. For the later lanthanides Ln=Tb–Lu, acetone solutions of Ln(NO 3) 3·6H 2O and Ph 3PO gave [Ln(Ph 3PO) 3(NO 3) 3] only, even with a large excess of Ph 3PO, but from cold ethanol [Ln(Ph 3PO) 4(NO 3) 2]NO 3 (Ln=Tb, Ho–Lu) were obtained. The structure of [Lu(Ph 3PO) 4(NO 3) 2]NO 3 shows an eight-coordinate metal centre with four phosphine oxides and two bidentate nitrate groups. In solution in CH 2Cl 2 or Me 2CO the tetrakis-complexes show varying amounts of decomposition into mixtures of [Ln(Ph 3PO) 3(NO 3) 3], [Ln(Ph 3PO) 4(NO 3) 2]NO 3 and Ph 3PO as judged by 31P{ 1H} NMR spectroscopy. The [Ln(Ph 3PO) 3(NO 3) 3] also partially decompose in solution for Ln=Dy–Lu, forming some tetrakis(phosphine oxide) species. 相似文献
5.
The new iodoammonium salts o-C 6H 4(NH 2) 2I +I − (1) and o-C 6H 4(NH 2) 2I + AsF 6− (2) were prepared by reaction of o-phenylene diamine with I 2 or I 3+AsF 6−, respectively. Compound 1 reacts with AlI 3 yielding quantitatively the corresponding tetraiodoaluminate o-C 6H 4(NH 2) 2I +AlI 4− (3). The species were characterized by chemical analysis, vibrational (IR and Raman) and temperature-dependent 1H NMR spectropscopy. Direct evidence for a N---I bond was found in the Raman spectra of 1, 2 and 3 (ν(NI) = 599–600 cm −1). 相似文献
6.
The reaction of [Nb(η 5-C 5H 4R) 2X 2] [1: R = SiMe 3, X = Cl; 2: R = SiMe 3, X = Br; 3: R = H, X = Cl; 4: R = t, X = Cl] with nitroso derivatives ArNO [ a: Ar = Ph; b: Ar = o-CH 3-C 3H 4; c: Ar = p-(CH 3) 2NC 6H 4] yields paramagnetic complexes formulated as [Nb(η 5-C 5H 4R)(η 3-C 5H 4R)X 2(ArNO- N, O) 1a, 1b, 1c, 2a, 3a, 4a and 4c, which have been characterized by ESR and IR spectroscopy. 相似文献
7.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
8.
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C 5H 5)CH 2(2-C 4H 3NH) (2) with Ti(NMe 2) 4 affords bis(dimethylamido)titanium complex [(η 5-C 5H 4)CH 2(2-C 4H 3N)]Ti(NMe 2) 2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH 2(2-C 4H 3NH)} 2C 5H 4 (4), undergoes an analogous reaction with Ti(NMe 2) 4 to give [1,3-{CH 2(2-C 4H 3N)} 2(η 5-C 5H 3)]Ti(NMe 2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
9.
Reaction of Me 3SiMe 2SiC 5H 5 (4), prepared from Me 3SiMe 2SiCl and C 5H 5Na, with Fe(CO) 5 in refluxing xylene afforded the title compound (3). The silicon-silicon bond in 3 is exceptionally stable in refluxing xylene and also in succeeding reactions to prepare a series of its derivatives. Thus, 3 reacted with I 2 in either chloroform or benzene, giving [η 5-Me 3SiMe 2SiC 5H 4Fe(CO) 2I] (6). Compound 3 was reduced by sodium amalgam and reacted subsequently with CH 3I, PhCH 2Cl, CH 3COCl, PhCOCl, Cy 3SnCl (Cy = cyclohexyl) and Ph 3SnCl, producing [η 5-Me 3SiMe 2SiC 5H 4Fe(CO) 2R][7 : R = CH 3 (a), PhCH 2 (b), CH 3CO (c), PhCO (d), Cy 3Sn (e) and Ph 3Sn (f), respectively]. The molecular structure of 3 has been determined by X-ray diffraction crystallography. It was found that 3 has a trans-configuration with a symmetrical centre located at the middle of the Fe---Fe bond. It is abnormal that the conformation of the disilane part around the Si---Si bond is almost eclipsed rather than staggered. 相似文献
10.
The reaction between Ru 2Cl(μ-O 2CCH 3) 4 and molten p-tert-butylbenzamide led to the formation of Ru 2Cl(μ-HNOCC 6H 4- p-CMe 3) 4. The polymeric structure of this insoluble compound was broken with AgBF 4, in anhydrous thf, giving [Ru 2(μ-HNOCC 6 H 4- p-CMe 3) 4(thf) 2]BF 4. The reaction of this cationic complex with OPPh 3 gave [Ru 2(μ-HNOCC 6H 4- p-CMe 3) 4(OPPh 3) 2]BF 4. The compounds have been characterized by elemental analysis, spectroscopic data and magnetic measurements and the crystal structure of [Ru 2(μ-HNOCC 6H 4- p-CMe 3) 4(OPPh 3) 2]BF 4 was determined by X-ray crystallography. The asymmetric unit is composed of halves of two different crystallographically independent centrosymmetric cations. Each ruthenium(II,III) dimer is bonded to four bridging p-tert-butylbenzamidate ligands and to two axial triphenylphosphine oxide molecules. The Ru---Ru distances in the two dimeric cations of the unit cell are 2.281(2) and 2.280(2) Å. The compound has a non-polar 2 : 2 arrangement of the tert-butylbenzamidate ligands. 相似文献
11.
An unexpected trimanganese(I) tetrathiolate-bridged complex, [Mn 3(CO) 9(μ-SC 6H 5) 4] −, with an incomplete cubane structure, was obtained by thermal reaction of [Mn 2(CO) 10] with [Mo(η 5-C 5H 5) 2(SC 6H 5) 2]. The structure, established by single-crystal X-ray diffraction studies, shows the cation, [Mo(η 5-C 5H 5) 2(H)CO] +, directed towards the vacant site of the cubane structure. Possible routes by which the anion and the cation could be formed are discussed. 相似文献
12.
Reaction of C 5H 4(SiMe 3) 2 with Mo(CO) 6 yielded [(η 5-C 5H 3(SiMe 3) 2)Mo(CO) 3] 2, which on addition of iodine gave [(η 5-C 5H 3(SiMe 3) 2Mo(CO) 3I]. Carbonyl displacement by a range of ligands: [L = P(OMe) 3, P(OPr i) 3,P(O- o-tol) 3, PMe 3, PMe 2Ph, PMePh 2, PPh 3, P( m-tol) 3] gave the new complexes [(η 5-C 5H 3(SiMe 3) 2 MO(CO) 2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of [(η 5-C 5H 3(SiMe 3) 2)Mo(CO) 2(L)I] L = PMe 2Ph, P(OMe) 3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L = P(OMe) 3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe 3 group) being the more stable isomer for L = P(OMe) 3. 相似文献
13.
The complex (di-η 5-C 5H 4CH 2CH 2CH 2C 5H 4)Ti(η 1-C 5H 5) 2 (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η 5-C 5H 5) 2 Ti(di-η 1-C 5H 4-CH 2CH 2CH 2C 5H 4) (I′) by the action of a convenient bridged dianion on (C 5H 5) 2 TiCl 2 afford several compounds, one of them is the complex I. The possibility of interconversion of these complexes by a fluctional process is discussed. 相似文献
14.
The behaviour of tetraarylstannanes, R 4Sn (R = C 6H 5CH 2, C 6H 5, o-, m-, p-CH 3C 6H 4), towards SO 2 under various conditions has now been studied in detail. Compared to aliphatic tetraorganostannanes, the variability of the reaction products is much less, so that in nearly all cases only disulfinates, R 2Sn(O 2SR) 2, are formed. The aromatic tin(IV) mono-, di- and tri-sulfinates are also obtained by metathetical reaction between the corresponding organotin halides and sodium sulfinates. A unique feature of triaryltin chlorides, R 3SnCl (R = C 6H 5, o-, m-, p-CH 3C 6H 4), is their disproportionation in liquid SO 2 leading to disulfinates, R 2Sn(O 2SR) 2, and dichlorides, R 2SnCl 2. ( p-CH 3C 6H 4) 2SnCl 2, under more efficient conditions, also accepts SO 2 forming ( p-CH 3C 6H 4SO 2) 2SnCl 2. The structural investigations of the newly prepared compounds are carried out on the basis of their IR and 1H NMR spectra. 相似文献
15.
The reaction of CpTiCl 3 with two equivalents of 1,2(LiS) 2C 6H 4 and one equivalent of Ph 4PBr in acetone/pentane affords the new anionic titanium(IV) complex [Ph 4P][CpTi(1,2-S 2C 6H 4) 2], which has been characterized by chemical analysis and by 1H NMR and IR spectroscopy. The structure of the five-coordinated, half-sandwich bis(dithiolato)titanate anion in the tetraphenyl phosphonium salt has been determined by an X-ray diffraction study. The anion has the two five-membered TiS 2C 2 chelate rings folded along the S---S axes by 36 and 23°, with one chelate ligand plane arranged exo, the other endo in relation to to the Cp ligand. 相似文献
16.
The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W 2(μ-H)(μ-Cl)(Cl 4(μ-dppm) 2 · (THF) 3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W 2(μ-H) 2(μ-O 2CC 6H 5) 2Cl 2(P(C 6H 5) 3) 2] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W 2(μ-H)(μ-Cl)Cl 4(μ-dppm) 2 · (THF) 3] (II), has been synthesized and the value of −2 J determined from variable-temperature 31P NMR spectroscopy. 相似文献
17.
Two organogold derivatives of diphenylmethane and diphenylethane, Ph 3PAu( o-C 6H 4)CH 2(C 6H 4- o)AuPPh 3 (1) and Ph 3PAu( o-C 6H 4)(CH 2) 2(C 6H 4- o)AuPPh 3 (2), have been synthesized by the reaction of ClAuPPh 3 with Li( o-C 6H 4)CH 2(C 6H 4- o)Li and Li( o-C 6H 4)(CH 2) 2(C 6H 4- o)Li respectively. The interaction of 1 with dppe results in the replacement of the two PPh 3 groups to give a macrocyclic compound (3) that includes an Au Au bond. Compounds 1 and 2 react with one or two equivalents of [Ph 3PAu]BF 4 to form new types of cationic complex [CH 2(C 6H 4- o) 2(AuPPh 3) 3]BF 4 (4), [CH 2(C 6H 4- o) 2(AuPPh 3) 4](BF 4) 2 (5), and [(CH 2) 2(C 6H 4- o) 2(AuPPh 3) 4](BF 4) 2 (6). Complexes 1–6 have been characterized by X-ray diffraction studies, FAB MS, and IR as well as by 1H and 31P NMR spectroscopy. A complicated system of Au H-C agostic interactions, involving the bridging alkyl groups (—CH 2— and CH 2-CH 2—) of diphenylmethane and diphenylethane ligands, has been found to occur in complexes 1–3 and 6. 相似文献
18.
Reactions of the lithium salts of 3-substituted indenes 1, 2 with ZrCl 4(THF) 2 gave two series of nonbridged bis(1-substituted)indenyl zirconocene dichloride complexes. Fractional recrystallization from THF–petroleum ether furnished the pure racemic and mesomeric isomers of [(η 5-C 9H 6-1-C(R 1)(R 2)--- o-C 6H 4---OCH 3) 2ZrCl 2]· nTHF (R 1=R 2=CH 3, n=1, rac-1a and meso-1b; R 1=CH 3, R 2=C 2H 5; n=0.5 or 0, rac-2a and meso-2b), respectively. Complex 1a was further characterized by X-ray diffraction to have a C2 symmetrically racemic structure, where the six-member rings of the indenyl parts are oriented laterally and two o-CH 3O---C 6H 4---C(CH 3) 2--- substituents are oriented to the open side of the metallocene (Ind: bis-lateral, anti; Substituent: bis-central, syn). The four zirconocene complexes are highly symmetrical in solution as characterized by room temperature 1H-NMR, however 1H– 1H NOESY of meso-1b shows that some of the NOE interactions arise from the two separated indenyl parts of the same molecule, which can only be well explained by taking into account the torsion isomers in solution. 相似文献
19.
The specific additions of one, three or four Ph 3PAu groups to [M(CO) 5] − (M=Mn, Re) are described. Thus [M(CO) 5] − in THF reacts with [(Ph 3PAu) 3O]BF 4 to give [(Ph 3PAu) 4Mn(CO) 4]BF 4. An X-ray crystal structure of the M = Mn example shows the cation to have a trigonal bipyramidal Au 4Mn core with the Mn in an equatorial site. The previously known neutral (Ph 3PAu) 3M(CO) 4 clusters are formed by addition of two Ph 3PAu groups, using the mixed reagent [(Ph 3PAu) 3O]BF 4/[ppn][Co(CO) 4], to Ph 3PAuM(CO) 5, which itself is readily prepared from [M(CO) 5] − and Ph 3PAuCl. 相似文献
20.
The ionic coupling of [Os 4H 2(CO) 12] 2− with [Ru( η6-C 6H 6)(MeCN) 3] 2+ affords the neutral mixed metal cluster Os 4Ru( μH) 2(CO) 12( η6-C 6H 6) 1. The reaction of 1 with trimethylphosphite leads to the initial formation of the addition product Os 4Ru( μH) 2(CO) 12( η6-C 6H 6)P(OMe) 3 2, but this complex rearranges in solution to give Os 4Ru( μ-H) 3(CO) 12( μ3- η6-C 6H 5)P(OMe) 3 3. An X-ray structure of 3 shows that the metal core of the cluster is a ruthenium-spiked Os 4 tetrahedron, with one hydrogen atom from the arene having transferred to the Os 4 core, and one arene carbon bridging an Os-Os edge, while the ring as a whole remains η6-bound to the Ru atom. 相似文献
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