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1.
Brian J. Rappoli Kenneth J. McGrath Clifford F. George John C. Cooper 《Journal of organometallic chemistry》1993,450(1-2):85-89
The ruthenium(II) complex Ru(CO)2(NH2(NH2CH2C6H5)2(Si(C6H5)(CH3)2)I has been prepared by the reaction of Ru(CO)4(Si(C6H5)(CH3)2)I with benzylamine. Two-dimensional homonuclear 1H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO)2(NH2CH2C6H5)2(Si(C6H5)(CH3)2)I·1/3C5H12 (triclinic; P
; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest. 相似文献
2.
Darryl P. Klein N. Quir s M ndez Jeffery W. Seyler Atta M. Arif J. A. Gladysz 《Journal of organometallic chemistry》1993,450(1-2):157-164
The crystal structures of propionaldehyde complex (RS,SR)-(η5-C5H5)Re(NO)(PPh3)(η2-O=CHCH2CH3)]+ PF6− (1b+ PF6s−; monoclinic, P21/c (No. 14), a = 10.166 (1) Å, b = 18.316(1) Å, c = 14.872(2) Å, β = 100.51(1)°, Z = 4) and butyraldehyde complex (RS,SR)-[(η5-C5H5)Re(NO)(PPh3)(η2-O=CHCH2CH2CH3)]+ PF6− (1c+PF6−; monoclinic, P21/a (No. 14), a = 14.851(1) Å, b = 18.623(3) Å, c = 10.026(2) Å, β = 102.95(1)°, Z = 4) have been determined at 22°C and −125°C, respectively. These exhibit C
O bond lengths (1.35(1), 1.338(5) Å) that are intermediate between those of propionaldehyde (1.209(4) Å) and 1-propanol (1.41 Å). Other geometric features are analyzed. Reaction of [(η5-C5H5)Re(NO)(PPh3)(ClCH2Cl)]+ BF4− and pivalaldehyde gives [(η5-C5H5)Re(NO)(PPh3)(η2-O=CHC(CH3)3)]+BF4− (81%), the spectroscopic properties of which establish a π C
O binding mode. 相似文献
3.
Hans Schumann 《Journal of organometallic chemistry》1985,290(3):c34-c36
The dinuclear organometallic compounds ((C5H5Fe(CO)2)2, CO2(CO)8 and (C5H5NiCO)2) are oxidized by [(C5H5)2Fe]X (X = BF4, PF6) in the presence of neutral ligands L to form the cationic organometallic complexes [C5H5Fe(CO)2L]X, [trans-Co(CO)3L2]X and [C5H5NiL2]X in high yield. 相似文献
4.
Racemic [C5H5Mo(CO)2LL]PF6, (2) with LL = 2-benzoylpyridine-1-phenylethylimine, undergoes spontaneous resolution upon crystallization from acetone/CH2Cl2/ethanol. The absolute configuration of the (+)546-isomer was shown to be (R) at the Mo atom and (R) at the asymmetric carbon atom. Comparison of 2 with [C5H5Mo(CO)2LL]PF6 (1) (LL = 2-carbaldehydepyridine-1-phenylethylimine) reveals distinct changes caused by the differences resulting from the presence of the phenyl group in 2 and the change from the (RR)- to the (RS)-configuration. 相似文献
5.
Reaction of optically active ketone complexes (+)-(R)-[(η5-C5H5)Re(NO)-(PPh3)(η1-O=C(R)(CH3)]+ BF4− (R = CH2CH3, CH(CH3)2m C(CH3)3, C6H5) with K(s-C4H9)3BH gives alkoxide complexes (+)-(RS)-(η5-C5H5)Re(NO)(PPh3)-(OCH(R)CH3) (73–90%) in 80–98% de. The alkoxide ligand is then converted to Mosher esters (93–99%) of 79–98% de. 相似文献
6.
María P. García M. Victoria Jimnez Teresa Luengo Luis A. Oro 《Journal of organometallic chemistry》1996,510(1-2):189-195
The reaction of the anionic mononuclear rhodium complex [Rh(C6F5)3Cl(Hpz)]t- (Hpz = pyrazole, C3H4N2) with methoxo or acetylacetonate complexes of Rh or Ir led to the heterodinuclear anionic compounds [(C6F5)3Rh(μ-Cl)(μ-pz)M(L2)] [M = Rh, L2 = cyclo-octa-1,5-diene, COD (1), tetrafluorobenzobarrelene, TFB (2) or (CO)2 (4); M = Ir, L2 = COD (3)]. The complex [Rh(C6F5)3(Hbim)]− (5) has been prepared by treating [Rh(C6F5)3(acac)]− with H2bim (acac = acetylacetonate; H2bim = 2,2′-biimidazole). Complex 5 also reacts with Rh or Ir methoxo, or with Pd acetylacetonate, complexes affording the heterodinuclear complexes [(C6F5)3Rh(μ-bim)M(L2)]− [M = Rh, L2 = COD (6) or TFB (7); M = Ir, L2 = COD (8); M = Pd, L2 = η3-C3H5 (9)]. With [Rh(acac)(CO)2], complex 5 yields the tetranuclear complex [{(C6F5)3Rh(μ-bim)Rh(CO)2}2]2−. Homodinuclear RhIII derivatives [{Rh(C6F5)3}2(μ-L)2]·- [L2 = OH, pz (11); OH, StBu (12); OH, SPh (13); bim (14)] have been obtained by substitution of one or both hydroxo groups of the dianion [{Rh(C6F5)3(μ-OH)}2]2− by the corresponding ligands. The reaction of [Rh(C6F5)3(Et2O)x] with [PdX2(COD)] produces neutral heterodinuclear compounds [(C6F5)3Rh(μ-X)2Pd(COD)] [X = Cl (15); Br (16)]. The anionic complexes 1–14 have been isolated as the benzyltriphenylphosphonium (PBzPh3+) salts. 相似文献
7.
Reaction of the optically active primary amine (S)-(—)--methylbenzylamine with trimethylaluminium in heptane affords the crystalline organoaluminium dimer (S)-(—)-(S)-(—)-[(C6H5)CH(CH3)NHA1(CH3)2]2. Isolated as large, colourless, extremely air-sensitive prismatic crystals, the title compound crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 8.406(3), b = 15.505(4), c = 17.547(5) Å, V = 2287 Å3 and p = 1.03 g cm−3 for Z = 4. Least-squares refinement based on 1477 observed reflections converged at R = 0.056, Rw = 0.058. Methane was eliminated during the course of the reaction due to cleavage of A1---C and N---H bonds resulting in an asymmetric A12N2 fragment at the core of the organoaluminium dimer. The mean A1---C bond distance in the dimethylaluminium units is 1.930(8), while the mean A1---N bond distance is 1.950(5) Å. Specific rotation ([]D25 in CH2C12)of the dimer is determined to be - 20.6°. 相似文献
8.
Mercedes Cano Jos A. Campo Margarita Panizo Jesús Tornero Nieves Menndex 《Polyhedron》1994,13(24):3309-3316
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO)3(CH3CN)2(Cl)(SnRCl2)] (R = Ph, Me) with P(4-XC6H4)3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO)2(CH3COCH3)2(PPh3)(Cl)(SnRCl2)]·nCH3COCH3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO)3{P(4-XC6H4)3}(μ-Cl)(SnRCl2)]2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO)3(CH3CN) {P(4-XC6H4)3}(Cl)(SnRCl2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
9.
S. Francis Amevor Hans-Ulrich Hund Albrecht Salzer 《Journal of organometallic chemistry》1996,520(1-2):79-84
A series of heterodimetallic complexes of general formula (C5R5)M(μ-CO)3RuC5Me5 (M = Cr, Mo, W; R = Me, Et) has been prepared in good yields by the reaction of [C5R5M(CO)3]− with [C5Me5Ru(CH3CN)3]+. (C5Me4Et)W(μ-CO)3Ru(C5Me5) was characterized by a crystal structure determination. The W---Ru bond length of 2.41 Å is consistent with the formulation of a metal-metal triple bond, while the unsymmetrical bonding mode of the three bridging carbonyl groups reflects the inherent non-equivalence of the two different C5R5M-units. Using [CpRu(CH3CN)3]+ or [CpRu(CO)2(CH3CN)]+ as the cationic precursor leads to the formation of dimetallic species (C5R5)M(CO)5RuC5H5 with both bridging and terminal carbonyl groups. 相似文献
10.
William J. Evans Roy A. Keyer Joseph W. Ziller 《Journal of organometallic chemistry》1993,450(1-2):115-120
The effects of cyclopentadienyl ring size on the geometry of bimetallic organosamarium complexes have been studied by comparing the X-ray crystal structure of [(C5H4Me)2(THF)Sm(μ-Cl)]2, prepared from KC5H4Me and SmCl3 in THF, with C5Me5 analogs. The complex crystallizes from THF at −30°C in space group Pbcn with a = 20.312(5), b = 9.626(2), c = 16.225(3) Å, V = 3172.5(12) Å3 and Dcalc = 1.74 g cm−3 for Z = 4. Least-squares refinement of the model based on 1759 reflections [|Fo| > 2.0σ(|Fo|)] converged to a final RF = 5.0%. The complex adopts a geometry which has a molecular two-fold rotation axis perpendicular to the Sm2Cl2 plane and a crystallographic inversion center. Hence, both methyl groups of each (C5H4Me)2Sm unit are located on the side opposite of the THF ligands, which are trans to each other, and the four C5H4Me ring centroids define a square plane. The Sm---Cl distances are 2.759(3) and 2.819(3) Å. 相似文献
11.
Eulalia Ramirez-Oliva Jorge Cervantes Francisco Cervantes-Lee Ramesh N. Kapoor Keith H. Pannell 《Journal of organometallic chemistry》1996,510(1-2):57-62
A transition metal-substituted silylacetylene [(η5-C5H5)Fe(CO)2SiMe2C]2, [FpMe2SiC]2 (I) was synthesized and characterized spectroscopically and structurally. I crystallized in the monoclinic space group P21/n, A = 13.011(3) Å B = 12.912(3) Å, C = 13.175(5) Å, β = 94.95(2). The acetylene linkage is reactive toward Co2(CO)8 to form I. Co2(CO)6 (II) which was also characterized spectroscopically and by single crystal X-ray diffraction. II crystallized in the orthorhombic space group Pbca, A = 17.64(2) Å, B = 14.225(10) Å, C = 24.49(2) Å. 相似文献
12.
Frank Rehbaum Karl-Heinz Thiele Sergej I. Trojanov 《Journal of organometallic chemistry》1991,410(3):327-333
Reduction of (C5H5)2TiCl2 with Zn in presence of benzyl cyanide gives the (μ-alkyl-ideneamido)titanocene complex [(C5H5)2TiCl]2[μ-{N=C(CH2C6H5)---C(CH2C6H5)=N}] with C---C bond formation between two benzyl cyanide molecules.
X-ray structure investigation indicates a symmetrical structure. The C=N distances are smaller than usual, the Ti---N distances are very short, and the Ti---N---C angle differs only a little from 180°, which infers a heteroallene structure of the complex. 相似文献
13.
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
14.
Won Seok Seo Youn Jaung Cho Sung Cheol Yoon Joon T. Park Younbong Park 《Journal of organometallic chemistry》2001,640(1-2):79-84
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)}2(η5-C5H3)]Ti(NMe2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
15.
Homochiral cyclopentane-based C1-symmetric P,P ligands C5H8(PPh2)(PR2) from C2-symmetric C5H8(PCl2)2
Treatment of 1,2-trans-C5H8(PCl2)2 with 1,2-C2H4(NHPr-i)2 gave the C2-symmetric perhydro-1,6,2,5-diazaphosphocine C5H8{P(Cl)N(Pr-i)CH2}2-cyclo, which produced dissymmetric C5H8(PPh2){P[N(Pr-i)CH2]2-cyclo} on further reaction with PhMgBr. Cleavage of the P---N bonds with gaseous HCl afforded C5H8(PPh2)(PCl2), which was converted to C5H8(PPh2){P(OPh)2}2 by reaction with phenol. All chiral P,P derivatives were obtained as racemates as well as resolved (1R,2R)- and (1S,2S)-enantiomers. 相似文献
16.
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
17.
Tat''yana V. Baukova Lyudmila G. Kuz''mina Natal''ya A. Oleinikova Dmitrii A. Lemenovskii Aleksander L. Blumenfel''d 《Journal of organometallic chemistry》1997,530(1-2):27-38
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.
Günter Urban Karlheinz Sünkel Wolfgang Beck 《Journal of organometallic chemistry》1985,290(3):329-339
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
19.
A single crystal of the azidoalane [Me2N(CH2)3]AltBu(N3) (1a), grown in a capillary using a miniature zone melting procedure, was investigated by X-ray analysis. Compound 1a (C9H21AlN4) is a monomeric species in the solid state, which crystallizes in the monoclinic space group P21 with a=6.8560(14) Å, b=12.251(3) Å, c=7.786(2) Å, β=108.51(3)° and Z=2. The results of the X-ray structural determination are compared with the calculated structure of 1a (HF/6-31G(d) and B3LYP/6-31G(d) level of theory). Whereas the overall agreement between the measured and calculated structure is good, the Al–N donor-bond length differs by 11 and 12 pm at the HF and B3LYP level, respectively. To evaluate the effects of a polar environment on the molecular structure of 1a self-consistent reaction field (SCRF) calculations at the HF and B3LYP level with the 6-31G(d) basis set were performed. 相似文献
20.
Erwan Le Grognec Rinaldo Poli Philippe Richard Rosa Llusar Santiago Uriel 《Journal of organometallic chemistry》2001,640(1-2):113-120
The reactions of the half-sandwich molybdenum(III) complexes CpMo(η4-C4H4R2)(CH3)2, where Cp=η5-C5H5 and R=H or CH3, with equimolar amounts of B(C6F5)3 have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe3. The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3], indicate that the borane attack has occurred at the methyl position. 相似文献