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1.
A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph3GeCHR1CHR2CO2)nSbAr(5−n) (R1=H, Ph; R2=H, CH3; n=1, 2) were synthesized and characterized by elemental analysis, IR, 1H-NMR, 13C-NMR and mass spectroscopy. The crystal structures of Ph3GeCH(Ph)CH2CO2SbPh4 and [Ph3GeCH2CH(CH3)CO2]2Sb(4-ClC6H4)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-C5H5)(CO)2LM-X (L = CO, PR3; M = Mo, W; X = BF4, PF6, AsF6, SbF6) react with H2S, p-MeC6H4SH, Ph2S and Ph2SO(L′) to give ionic complexes [(π-C5H5)(CO)2LML′]+ X. Also sulfur-bridged complexes, [(π-C5H5)(CO)3W---SH---W(CO)3(π-C5H5)]+ AsF6 and [(π-C5H5)(CO)3M-μ-S2C=NCH2Ph-M(CO)3(π-C5H5)], have been obtained. Reactions with SO2 and CS2 have been examined.  相似文献   

3.
The interaction of [(η5-C5H4But)2YbCl · LiCl] with one equivalent of Li[(CH2) (CH2)PPh2] in tetrahydrofuran gave [Ph2PMe2][(η5-C5H4But)2Li] (1) and [(η5-C5H4But)2Yb(Cl)CH2P(Me)Ph2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph2PMe2][CF3SO3] with two equivalents of (C5H4But)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 [(η5-C5H4But)2Li] anion.  相似文献   

4.
The reaction of Ln(NO3)3·6H2O (Ln=La, Ce, Pr or Nd) with a sixfold excess of Ph3PO in acetone formed [Ln(Ph3PO)4(NO3)3]·Me2CO. 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 CH2Cl2 or Me2CO solutions, 31P NMR studies show that the complexes are essentially completely decomposed into [Ln(Ph3PO)3(NO3)3] and Ph3PO. Similar reactions in ethanol gave [Ln(Ph3PO)3(NO3)3] only. In contrast for Ln=Sm, Eu or Gd, only the [Ln(Ph3PO)3(NO3)3] are formed from either acetone or ethanol solutions. For the later lanthanides Ln=Tb–Lu, acetone solutions of Ln(NO3)3·6H2O and Ph3PO gave [Ln(Ph3PO)3(NO3)3] only, even with a large excess of Ph3PO, but from cold ethanol [Ln(Ph3PO)4(NO3)2]NO3 (Ln=Tb, Ho–Lu) were obtained. The structure of [Lu(Ph3PO)4(NO3)2]NO3 shows an eight-coordinate metal centre with four phosphine oxides and two bidentate nitrate groups. In solution in CH2Cl2 or Me2CO the tetrakis-complexes show varying amounts of decomposition into mixtures of [Ln(Ph3PO)3(NO3)3], [Ln(Ph3PO)4(NO3)2]NO3 and Ph3PO as judged by 31P{1H} NMR spectroscopy. The [Ln(Ph3PO)3(NO3)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-C6H4(NH2)2I+I (1) and o-C6H4(NH2)2I+ AsF6 (2) were prepared by reaction of o-phenylene diamine with I2 or I3+AsF6, respectively. Compound 1 reacts with AlI3 yielding quantitatively the corresponding tetraiodoaluminate o-C6H4(NH2)2I+AlI4 (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(η5-C5H4R)2X2] [1: R = SiMe3, X = Cl; 2: R = SiMe3, X = Br; 3: R = H, X = Cl; 4: R =t, X = Cl] with nitroso derivatives ArNO [a: Ar = Ph; b: Ar = o-CH3-C3H4; c: Ar = p-(CH3)2NC6H4] yields paramagnetic complexes formulated as [Nb(η5-C5H4R)(η3-C5H4R)X2(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)(PPh3)2] (Ar = C6H5, C6F5, 2-C6H4CH3, 3-C6H4CH3, 4-C6H4CH3, 2-C6H4OCH3, 2,6-C6H3-(OCH3)2, 4-C6H4N(CH3)2, 3-C6H4Cl, 4-C6H4Cl, 4-C6H4Cl, 3-C6H4CF3, 4-C6H4CF3) 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 (C5H5)CH2(2-C4H3NH) (2) with Ti(NMe2)4 affords bis(dimethylamido)titanium complex [(η5-C5H4)CH2(2-C4H3N)]Ti(NMe2)2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH2(2-C4H3NH)}2C5H4 (4), undergoes an analogous reaction with Ti(NMe2)4 to give [1,3-{CH2(2-C4H3N)}25-C5H3)]Ti(NMe2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies.  相似文献   

9.
Reaction of Me3SiMe2SiC5H5 (4), prepared from Me3SiMe2SiCl and C5H5Na, 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 I2 in either chloroform or benzene, giving [η5-Me3SiMe2SiC5H4Fe(CO)2I] (6). Compound 3 was reduced by sodium amalgam and reacted subsequently with CH3I, PhCH2Cl, CH3COCl, PhCOCl, Cy3SnCl (Cy = cyclohexyl) and Ph3SnCl, producing [η5-Me3SiMe2SiC5H4Fe(CO)2R][7 : R = CH3 (a), PhCH2 (b), CH3CO (c), PhCO (d), Cy3Sn (e) and Ph3Sn (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 Ru2Cl(μ-O2CCH3)4 and molten p-tert-butylbenzamide led to the formation of Ru2Cl(μ-HNOCC6H4-p-CMe3)4. The polymeric structure of this insoluble compound was broken with AgBF4, in anhydrous thf, giving [Ru2(μ-HNOCC6 H4-p-CMe3)4(thf)2]BF4. The reaction of this cationic complex with OPPh3 gave [Ru2(μ-HNOCC6H4-p-CMe3)4(OPPh3)2]BF4. The compounds have been characterized by elemental analysis, spectroscopic data and magnetic measurements and the crystal structure of [Ru2(μ-HNOCC6H4-p-CMe3)4(OPPh3)2]BF4 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, [Mn3(CO)9(μ-SC6H5)4], with an incomplete cubane structure, was obtained by thermal reaction of [Mn2(CO)10] with [Mo(η5-C5H5)2(SC6H5)2]. The structure, established by single-crystal X-ray diffraction studies, shows the cation, [Mo(η5-C5H5)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 C5H4(SiMe3)2 with Mo(CO)6 yielded [(η5-C5H3(SiMe3)2)Mo(CO)3]2, which on addition of iodine gave [(η5-C5H3(SiMe3)2Mo(CO)3I]. Carbonyl displacement by a range of ligands: [L = P(OMe)3, P(OPri)3,P(O-o-tol)3, PMe3, PMe2Ph, PMePh2, PPh3, P(m-tol)3] gave the new complexes [(η5-C5H3(SiMe3)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 [(η5-C5H3(SiMe3)2)Mo(CO)2(L)I] L = PMe2Ph, 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 SiMe3 group) being the more stable isomer for L = P(OMe)3.  相似文献   

13.
The complex (di-η5-C5H4CH2CH2CH2C5H4)Ti(η1-C5H5)2 (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η5-C5H5)2 Ti(di-η1-C5H4-CH2CH2CH2C5H4) (I′) by the action of a convenient bridged dianion on (C5H5)2 TiCl2 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, R4Sn (R = C6H5CH2, C6H5, o-, m-, p-CH3C6H4), towards SO2 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, R2Sn(O2SR)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, R3SnCl (R = C6H5, o-, m-, p-CH3C6H4), is their disproportionation in liquid SO2 leading to disulfinates, R2Sn(O2SR)2, and dichlorides, R2SnCl2. (p-CH3C6H4)2SnCl2, under more efficient conditions, also accepts SO2 forming (p-CH3C6H4SO2)2SnCl2. 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 CpTiCl3 with two equivalents of 1,2(LiS)2C6H4 and one equivalent of Ph4PBr in acetone/pentane affords the new anionic titanium(IV) complex [Ph4P][CpTi(1,2-S2C6H4)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 TiS2C2 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 W2(μ-H)(μ-Cl)(Cl4(μ-dppm)2 · (THF)3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W2(μ-H)2(μ-O2CC6H5)2Cl2(P(C6H5)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, [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2 · (THF)3] (II), has been synthesized and the value of −2J determined from variable-temperature 31P NMR spectroscopy.  相似文献   

17.
Two organogold derivatives of diphenylmethane and diphenylethane, Ph3PAu(o-C6H4)CH2(C6H4-o)AuPPh3 (1) and Ph3PAu(o-C6H4)(CH2)2(C6H4-o)AuPPh3 (2), have been synthesized by the reaction of ClAuPPh3 with Li(o-C6H4)CH2(C6H4-o)Li and Li(o-C6H4)(CH2)2(C6H4-o)Li respectively. The interaction of 1 with dppe results in the replacement of the two PPh3 groups to give a macrocyclic compound (3) that includes an Au Au bond. Compounds 1 and 2 react with one or two equivalents of [Ph3PAu]BF4 to form new types of cationic complex [CH2(C6H4-o)2(AuPPh3)3]BF4 (4), [CH2(C6H4-o)2(AuPPh3)4](BF4)2 (5), and [(CH2)2(C6H4-o)2(AuPPh3)4](BF4)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 (—CH2— and CH2-CH2—) 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 ZrCl4(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 [(η5-C9H6-1-C(R1)(R2)---o-C6H4---OCH3)2ZrCl2nTHF (R1=R2=CH3, n=1, rac-1a and meso-1b; R1=CH3, R2=C2H5; 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-CH3O---C6H4---C(CH3)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 Ph3PAu groups to [M(CO)5] (M=Mn, Re) are described. Thus [M(CO)5] in THF reacts with [(Ph3PAu)3O]BF4 to give [(Ph3PAu)4Mn(CO)4]BF4. An X-ray crystal structure of the M = Mn example shows the cation to have a trigonal bipyramidal Au4Mn core with the Mn in an equatorial site. The previously known neutral (Ph3PAu)3M(CO)4 clusters are formed by addition of two Ph3PAu groups, using the mixed reagent [(Ph3PAu) 3O]BF4/[ppn][Co(CO)4], to Ph3PAuM(CO)5, which itself is readily prepared from [M(CO)5] and Ph3PAuCl.  相似文献   

20.
The ionic coupling of [Os4H2(CO)12]2− with [Ru(η6-C6H6)(MeCN)3]2+ affords the neutral mixed metal cluster Os4Ru(μH)2(CO)12(η6-C6H6) 1. The reaction of 1 with trimethylphosphite leads to the initial formation of the addition product Os4Ru(μH)2(CO)12(η6-C6H6)P(OMe)3 2, but this complex rearranges in solution to give Os4Ru(μ-H)3(CO)12(μ3-η6-C6H5)P(OMe)3 3. An X-ray structure of 3 shows that the metal core of the cluster is a ruthenium-spiked Os4 tetrahedron, with one hydrogen atom from the arene having transferred to the Os4 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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