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1.
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
2.
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
3.
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
4.
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
5.
The mechanism of the transformation of (η 5-C 5H 5) 2NbCl 2 to (η 5-C 5H 5) 2NbH 3 by hydridoaluminate reducing agents has been investigated. Results suggest disproportionation of a niobium(IV) hydrite, leading to the trihydride product and a niobium(III) hydridoaluminate, (η 5-C 5H 5) 2NbH 2AlR 2, which in turn is converted to the trihydride on hydrolysis. (η 5-C 5H 5) 2NbH 2AlH 2 has been isolated; deuterium labelling shows that hydrogens exchange between ring and metal-bridging positions in this molecule. 相似文献
6.
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
7.
Reaction of optically active ketone complexes (+)-( R)-[(η 5-C 5H 5)Re(NO)-(PPh 3)(η 1-O=C(R)(CH 3)] + BF 4− (R = CH 2CH 3, CH(CH 3) 2m C(CH 3) 3, C 6H 5) with K(s-C 4H 9) 3BH gives alkoxide complexes (+)-( RS)-(η 5-C 5H 5)Re(NO)(PPh 3)-(OCH(R)CH 3) (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
8.
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
9.
The silyl group migration observed upon treating ( R)(+)-(η 5-C 5H 5)Fe(CO) 2-SiMePh(1-Np) with n-BuLi occurs with retention of configuration at silicon. The anion resulting from the migration, (η 5-C 5H 4SiMePh(1-Np))Fe(CO) 2Li, is alkylated with MeI to give ( R)-(−)-(η 5-C 5H 4SiMePh(1-Np))Fe(CO) 2Me (II). Compound II is independently prepared from (η 5-C 5H 5)Fe(CO) 2Me. A concerted mechanism for the migration involving frontside nucleophilic attack at silicon is suggested. 相似文献
10.
The complex [MoW(μ-CC 6H 4Me-4)(CO) 2(η 7-C 7H 7)(η 5-C 2B 9H 10Me)] reacts with diazomethane in Et 2O containing EtOH to afford the dimetal compound [MoW(OEt)(μ-CH 2){μ-C(C 6H 4Me-4)C(Me)O}(η 7-C 7H 7)(η 5-C 2B 9H 10Me)]. The structure of this product was established by X-ray diffraction. The Mo---W bond [2.778(4) Å] is bridged by a CH 2 group [μ-C---Mo 2.14(3), μ-C---W 2.02(3) Å] and by a C(C 6H 4Me-4)C(Me)O fragment [Mo---O 2.11(3), W---O 2.18(2), Mo---C(C 6H 4Me-4) 2.41(3), W---C(C 6H 4Me-4) 2.09(3), Mo---C(Me) 2.26(3) Å]. The molybdenum atom is η 7-coordinated by the C 7H 7 ring and the tungsten atom is η 5-coordinated by the open pentagonal face of the nido-icosahedral C 2B 9H 10Me cage. The tungsten atom also carries a terminally bound OEt group [W---O 1.88(3) Å]. The 1H and 13C-{ 1H} NMR data for the dimetal compound are reported and discussed. 相似文献
11.
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
12.
The reactions of the half-sandwich molybdenum(III) complexes CpMo(η 4-C 4H 4R 2)(CH 3) 2, where Cp=η 5-C 5H 5 and R=H or CH 3, with equimolar amounts of B(C 6F 5) 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 PMe 3. The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η 4-C 4H 6)(μ-Cl)(μ-CH 2)(O)MoCp][CH 3B(C 6F 5) 3], indicate that the borane attack has occurred at the methyl position. 相似文献
13.
The crystal structures of propionaldehyde complex ( RS, SR)-(η 5-C 5H 5)Re(NO)(PPh 3)(η 2-O=CHCH 2CH 3)] + PF 6− (1b + PF 6s−; monoclinic, P2 1/ 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)-[(η 5-C 5H 5)Re(NO)(PPh 3)(η 2-O=CHCH 2CH 2CH 3)] + PF 6− (1c +PF 6−; monoclinic, P2 1/ 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 [(η 5-C 5H 5)Re(NO)(PPh 3)(ClCH 2Cl)] + BF 4− and pivalaldehyde gives [(η 5-C 5H 5)Re(NO)(PPh 3)(η 2-O=CHC(CH 3) 3)] +BF 4− (81%), the spectroscopic properties of which establish a π C
O binding mode. 相似文献
14.
The tetrahedral heteronuclear cluster complex (η 5-C 5H 5) 2W 2Ir 2(CO) 10 reacts with N 2CHCO 2R (R = Et, Me) at room temperature to form the dicarbene species (η 5-C 5H 5) 2W 2Ir 2(CO) 7(CHCO 2R) 2. An X-ray diffraction study (R = Et) shows an intact tetrahedral metal framework with two distinct sites for the CHCO 2Et ligands. The first uses its carbon atom to bridge the Ir---Ir bond; the second uses its carbon atom to bridge an Ir---W bond and, additionally, forms a donor bond from a carbonyl oxygen atom to the second tungsten atom. 相似文献
15.
Syntheses of the novel sandwich compounds [Fe(η 5-C 5H 5)(η 5-C 2R 2P 3)] and [Fe(η 5-C 5H 5)(η 5-C 2R 2P 3)W(CO) 5], (R = Bu t), are described. The mode of attachment of the [W(CO) 5] fragment in the latter compound has been determined by NMR and single crystal X-ray diffraction studies. 相似文献
16.
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
17.
The photochemical reactions of the title complexes were studied in air-free benzene solution. In both cases photolysis leads to the production of complexes of the formula (η 5-C 5H 5)M(PPh 3) 2. Both reactions are the result of the initial loss of a methyl radical from the excited state. The primary photoproduct, (η 5-C 5H 5)MPPh 3 (M=CO, Ni), then scavenges neutral ligands from the solution to yield, in the case of PPh 3, (η 5-C 5H 5)M(PPh 3) 2. In the absence of uncoordinated ligand in the reaction solution, the cobalt derivative reacts with the starting material to yield (η 5-C 5H 5)Co(PPh 3) 2, a methyl radical and (η 5-C 5H 5)Co(solvent) n. 相似文献
18.
A high yield synthesis of the carbonyl dithiocarbamato derivative Fe(CO) 2(η 2-S 2CNMe 2) 2 and Fe(η 2-S 2CNMe 2) 2 by photolysis with visible light of solutions containing Fe 2(CO) 9 or Fe 3(CO) 12 and [(η 5-C 5H 5)(CO) 3W(η 1-SCSNMe 2)] is reported. 相似文献
19.
Reaction of YbI 2 with two equivalents of cyclopentylindenyl lithium (C 5H 9C 9H 6Li) affords ytterbium(II) substituted indenyl complex (C 5H 9C 9H 6) 2Yb(THF) 2 (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI 2 and cyclopentylcyclopentadienyl sodium (C 5H 9C 5H 4Na) gives complex [(C 5H 9C 5H 4) 2Yb(THF)] 2O 2 (2) in the presence of a trace amount of O 2, the molecular structure of which comprises two (C 5H 9C 5H 4) 2Yb(THF) bridged by an asymmetric O 2 unit. The O 2 unit and ytterbium atoms define a plane that contains a Ci symmetry center. 相似文献
20.
The structures of the versatile starting compounds for organoiron complexes, the cationic aqua complex [(η 5-C 5Me 4Et)Fe(CO) 2(OH 2)]BF 4 (1b) and the halide complexes (η 5-C 5Me 5)Fe(CO) 2-I (2a), (η 5-C 5Me 4Et)Fe(CO) 2-I (2b) and (η 5-C 5Me 4Et)Fe(CO) 2-Cl (3b), are characterized by X-ray crystallography. Complex 1b [Fe---O: 2.022(8) Å and 2.043(9) Å, two independent molecules] is the first structurally characterized example of organoiron aqua complexes. Details of the synthetic procedures for the above complexes and the labile cationic THF complexes [η 5-C 5R 5)Fe(CO) 2(THF)]BF 4 (4) are disclosed, and the dissociation equilibrium of 4 is confirmed by means of variable temperature 1H-NMR as well as saturation transfer experiment. 相似文献
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