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1.
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
2.
Reduction of (C 5H 5) 2TiCl 2 with Zn in presence of benzyl cyanide gives the (μ-alkyl-ideneamido)titanocene complex [(C 5H 5) 2TiCl] 2[μ-{N=C(CH 2C 6H 5)---C(CH 2C 6H 5)=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
3.
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
4.
The ruthenium(II) complex Ru(CO) 2(NH 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I has been prepared by the reaction of Ru(CO) 4(Si(C 6H 5)(CH 3) 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(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I·1/3C 5H 12 (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
5.
The synthesis of the potential bridging ligand (C 6H 5) 2PCH 2CH 2Si(CH 3) 2C 5H 4 (3) is described. The ferrocene (6 derived from 3 has been found to form macrocyclic complexes with metal fragments NiCl 2, NiBr 2, and Co 2(CO) 6. Although monomeric, bimetallic products might have been expected based upon the reduced steric demands of ligand 3 relative to an analogous ligand, (C 6H 5) 2PCH 2Si(CH) 3) 2C 5H 4 (1), it appears that the increased flexibility in 3 is the overriding factor leading to a preference for inter- rather than intramolecular coordination of the second phosphine function in 6. 相似文献
6.
The diphenylbutadiene-bridged gadolinium complex [GdCl 2(THF) 3] 2( μ-Ph 2C 4H 4) · 3THF (1) has been obtained by the reaction of Gd(III) chloride with diphenylbutadienepotassium. The molecular structure of 1 was determined by X-ray diffraction. The complex 1 has a binuclear structure in which a bridging diphenylbutadiene ligand is η4-bonded to the Gd atoms connecting two GdCl 2(THF) 3 units. Both Gd atoms have a distorted octahedral environment. At the Gd atom the two Cl atoms are in trans positions and the four other coordination sites are occupied by the three O atoms of THF molecules and the η4-bonded C 4H 4 fragment of a diphenylbutadiene ligand. In the two η4-bonded GdC 4H 4 fragments one of the Gd-C η4-distances is significantly elongated (2.86(3) and 2.97(3) Å) compared with other three (2.65(3)–2.69(3) and 2.67(3)—2.77(3) Å). The magnetic moment of Gd, equal to 8.1 BM, is typical for Gd 3+ compounds that is evidence for a formal charge of DPBD ligand of −2 in complex 1. However, the expected distribution of the C-C bond of the diene fragment as long—short—long is not realized. 相似文献
7.
The effects of cyclopentadienyl ring size on the geometry of bimetallic organosamarium complexes have been studied by comparing the X-ray crystal structure of [(C 5H 4Me) 2(THF)Sm(μ-Cl)] 2, prepared from KC 5H 4Me and SmCl 3 in THF, with C 5Me 5 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) Å 3 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 Sm 2Cl 2 plane and a crystallographic inversion center. Hence, both methyl groups of each (C 5H 4Me) 2Sm unit are located on the side opposite of the THF ligands, which are trans to each other, and the four C 5H 4Me ring centroids define a square plane. The Sm---Cl distances are 2.759(3) and 2.819(3) Å. 相似文献
8.
The reaction of LnCl_3 with K _9H_7(C_9H_7=indenyl)andK_2C_8H_8(C_8H_8=cyclooctatetraene)in tetrahydrofuran(THF)give thecorresponding complexes(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF.The synthesis of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF(Ln=Pr,Nd)and crystal structure of(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF are described. 相似文献
9.
Thermal displacement of coordinated nitriles RCN (R = CH 3, C 2H 5 or n-C 3H 7) in [C 5H 5Fe(L 2)(NCR)]X complexes (L 2 = P(OCH 3) 3) 2, (P(OC 6H 5) 3) 2 or (C 6H 5) 2PC 2H 4P(C 6H 5) 2 (DPPE)) by E(CH 3) 2 affords high yields of [C 5H 5Fe(L 2)(E(CH 3) 2)]X compounds (E = S, Se and Te; X = BF 4 or PF 6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C 5H 5Fe(CO) 2(E(CH 3) 2)]BF 4 compounds. The molecular structure of [C 5H 5Fe(P(OCH 3) 3) 2(S(CH 3) 2)]PF 6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2 1/ n- C52h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å. 相似文献
10.
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
11.
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
12.
The complex C 5H 5(PMe 3)Co(μ-CS) 2CoC 5H 5 (I) is formed by the reaction of C 5H 5Co(PMe 3)CS and CH 2I 2. The X-ray structure analysis shows an unsymmetrical non-planar Co 2C 2-skeleton with different Co---C bond lengths. The Co---Co distance is 239.2 pm. Compound I thus represents a new example of binuclear (18 + 16)-electron complexes in which the more electron-rich metal atom forms a donor bond to the more electron-poor counterpart. The reaction of I with ligands such as P(NMe 2) 3 does not lead to bridge cleavage indicating the stability of the Co(CS) 2Co-framework. 相似文献
13.
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
14.
The reaction between RMgCl (two equivalents) and 1,2-W 2Cl 2(NMe 2) 4 in hydrocarbon solvents affords the compounds W 2R 2(NMe 2) 4, where R = allyl and 1− and 2-methyl-allyl. In the solid state the molecular structure of W 2(C 3H 5) 2(NMe 2) 4 has C2 symmetry with bridging allyl ligands and terminal W---NMe 2 ligands. The W---W distance 2.480(1) Å and the C---C distances, 1.47(1) Å, imply an extensive mixing of the allyl π-MOs with the WW π-MOs, and this is supported by an MO calculation on the molecule W 2(C 3H 5) 2(NH 2) 4 employing the method of Fenske and Hall. The most notable interaction is the ability of the (WW) 6+ centre to donate to the allyl π *-MO (π 3). This interaction is largely responsible for the long W---W distance, as well as the long C---C distances, in the allyl ligand. The structure of the 2-methyl-allyl derivative W 2(C 4H 7) 2(NMe 2) 4 in the solid state reveals a gauche-W 2C 2N 4 core with W---W = 2.286(1) Å and W---C = 2.18(1) Å, typical of WW and W---C triple and single bonds, respectively. In solution (toluene-d 8) 1H and 13C NMR spectra over a temperature range −80°C to +60°C indicate that both anti- and gauche- W 2C 2N 4 rotamers are present for the 2-methyl-allyl derivative. In addition, there is a facile fluxional process that equilibrates both ends of the 2-methyl-allyl ligand on the NMR time-scale. This process leads to a coalescence at 100°C and is believed to take place via an η 3-bound intermediate. The 1-methyl-allyl derivative also binds in an η 1 fashion in solution and temperature-dependent rotations about the W---N, W---C and C=C bonds are frozen out at low temperatures. The spectra of the allyl compound W 2(C 3H 5) 2(NMe 2) 4 revealed the presence of two isomers in solution—one of which can be readily reconciled with the presence of the bridging isomer found in the solid state while the other is proposed to be W 2(η 3-C 3H 5) 2(NMe 2) 4. The compound W 2R 2(NMe 2) 4 where R = 2,4-dimethyl- pentadiene was similarly prepared and displayed dynamic NMR behaviour explainable in terms of facile η 1 = η 3 interconversions. 相似文献
15.
Treatment of 1,2- trans-C 5H 8(PCl 2) 2 with 1,2-C 2H 4(NHPr- i) 2 gave the C2-symmetric perhydro-1,6,2,5-diazaphosphocine C 5H 8{P(Cl)N(Pr- i)CH 2} 2- cyclo, which produced dissymmetric C 5H 8(PPh 2){P[N(Pr- i)CH 2] 2- cyclo} on further reaction with PhMgBr. Cleavage of the P---N bonds with gaseous HCl afforded C 5H 8(PPh 2)(PCl 2), which was converted to C 5H 8(PPh 2){P(OPh) 2} 2 by reaction with phenol. All chiral P, P derivatives were obtained as racemates as well as resolved (1 R,2 R)- and (1 S,2 S)-enantiomers. 相似文献
16.
The reaction of[CpMo(CO)_2]_2 with 8,8'-diquinolyl disulphideC_9H_6NSSNC_9H_6 resulted in the cleavage of Mo≡Mo triple bond to give a newnononuclear complex CpMo(CO)_2(N,S-C_9H_6NS)which was refluxed with PPh_3 inTHF to form the title complex.The crystal structure of the title complexwas determined by X-ray diffraction. 相似文献
17.
The structure of the (C 18H 8Se 3O 2) 2(C 6H 5CN) molecular complex isolated from the TSeT + HgI 2 reaction in benzonitrile has been determined. The -Se-Se-Se- fragment has been found to have Se---Se bond lengths equal to 2.348(3) and 2.350(4) Å. 相似文献
18.
Naphthaleneytterbium, C 10H 8Yb(THF) 3, reacts with Cp 2Cr, Cp 2Co, Cp 2Ni, and Cp 2V in THF to give Cp 2Yb. In the case of the reaction of C 10H 8Yb(THF) 3 with Cp 2V, vanadium-containing intermediates could be isolated. One of them, CpVC 10H 8VCp, has been characterized by X-ray diffraction. The crystals are monoclinic, space group P2 1/ n, with a 907.0(5), b 798.8(3), c 1080.8(5) pm, β 105.21(4)°; Z = 2. The structure was refined to R = 0.0288 for 1131 observed reflections ( Fo > 4σ( Fo)). 相似文献
19.
(C 5Me 5) 2Sm(THF) 2 reacts with 1,2-epoxybutane in toluene to form, in addition to the toluene soluble [(C 5 Me 5) 2Sm] 2(μ-O), 1, the hexane soluble [(C 5Me 5) 2Sm(THF)] 2(μ-O), 2. In hexane, 2 loses THF to form 1 as a precipitate, but 1 cannot be converted to 2 by addition of THF at room temperature. Compound 1 does convert to 2 in low yield in THF at reflux. The reaction of (C 5Me 5) 2SM(phthalan) with 1,2-epoxybutane generates 1 and a phthalan analog of 2, [(C 5Me 5) 2Sm(phthalan)] 2(μ,-O), 3. Compound 2 reacts with Me 3CCN to form [(C 5Me 5) 2Sm(NCCMe 3)] 2(μ-O), 4, by displacement of THF. 相似文献
20.
Nine complexes(RC_5H_4)_2Ti(O_2CC_6H_4X)_2(R=H,CH_3;X=H,o-Cl,o-OH,o-NH_2,o-NHPh)have been conveniently prepared by the reaction of(RC_5H_4)_2TiCl_2 with 2 equiv.sodium salts of corresponding carboxylic acidin aqueous solution containing acetylacetone.The carboxylate ligands inthe complexes coordinate to titanium atom in monodentate mode. 相似文献
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