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1.
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
2.
The η 3-allyliridium complexes [Ir(η 3-2-RC 3H 4)(P iPr 3) 2] (2, 3) have been prepared in a one-pot reaction from [IrCl(C 2H 4) 2] 2, 2-RC 3H 4Li and P iPr 3 in 70% yield. Compounds 2 and 3 react spontaneously with H 2 to give [IrH 5(P iPr 3) 2] (7) and with excess PhC=CH and MeCCH to give [Ir(CCPh) 3(P iPr 3) 2] (5) and [Ir(CCMe) 2(CMe=CH 2)(P iPr 3) 2] (6), respectively. From 2 (or 3) and two equivalents of PhCCH the complex [IrH(CCPh) 2(P iPr 3) 2] (4) has been obtained. Treatment of 2 or 3 with CF 3CO 2H does not lead to a cleavage of the allyl-metal bond but affords the allyl(hydrido)-iridium(III) complexes [IrH(η 3-2-RC 3H 4)(η 1-P 2CCF 3)(P iPr 3) 2] (8, 9) in almost quantitative yield. 相似文献
3.
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
4.
The interaction between Mo 2(O 2CCH 3) 4, Me 3SiI and I 2 in THF resulted in oxygen abstraction from the solvent and formation of [Mo 2(μ-O)(μ-I)(μ-O 2CCH 3) I 2(THF) 4] +[MoOI 4(THF)] − and I---(CH 2) 4---I. The molybdenum complex has been characterized by X-ray diffractometry. Crystal data: triclinic, space group P
, a = 13.827(3) Å; b = 15.803(7) Å; c = 9.950(3) Å; = 93.34(4)°; β = 102.40(2)°; γ = 90.09(2)°; V = 2120(2) Å 3; Z = 2; dcalc = 2.559 g cm −3; R = 0.0476 ( Rw = 0.0613) for 370 parameters and 3938 data with F02> 3σ( F02). The metal-metal distance in the cation is 2.527(2) Å and indicates a strong interaction. The magnetic behavior is consistent with the assignment of one unpaired electron to the Mo 27+ core of the cation and one to the d1 Mo(V) center of the anion. The interaction between Mo(CO) 6 and I 2 in THF also results in the formation of 1,4-diiodobutane. 相似文献
5.
The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen 2) 2V 4O 12]·5H 2O (1) and [Ni(phen) 3] 2[V 4O 12]·17.5H 2O (2). Crystal data: C 48H 52Cd 2N 8O 22V 4 (1), triclinic.
a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C 72H 131N 12Ni 2O 29.5V 4 (2), triclinic.
a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V 4O 12] 4− cluster covalently attached to two {Cd(phen) 2} 2+ fragments, in which the [V 4O 12] 4− cluster adopts a chair-like configuration. In the structure of 2, the [V 4O 12] 4− cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V 4O 12] 4− unit and crystallization water molecules. 相似文献
6.
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
7.
The compound [RU 3(μ 3,η 2- -ampy)(μ 3η 1:η 2-PhC=CHPh)(CO) 6(PPh 3) 2] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU 3(η-H)(μ 3,η 2- ampy) (μ,η 1:η 2-PhC=CHPh)(CO) 7(PPh 3)] with triphenylphosphine at room temperature. However, the reaction of [RU 3(μ-H)(μ 3, η 2 -ampy)(CO) 7(PPh 3) 2] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU 3(μ 3,η 2-ampy)(μ,η 1:η 2 -PhC=CHPh)(μ,-PPh 2)(Ph)(CO) 5(PPh 3)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H 2), although progressive deactivation of the catalytic species is observed. The dihydride [RU 3(μ-H) 2(μ 3,η 2-ampy)(μ,η 1:η 2- PhC=CHPh)(CO) 5(PPh 3) 2] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction. 相似文献
8.
The reactions of the diruthenium carbonyl complexes [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)]X (X=BF 4− (1a) or PF 6− (1b)) with neutral or anionic bidentate ligands (L,L) afford a series of the diruthenium bridging carbonyl complexes [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-(L,L)) 2]X n ((L,L)=acetate (O 2CMe), 2,2′-bipyridine (bpy), acetylacetonate (acac), 8-quinolinolate (quin); n=0, 1, 2). Apparently with coordination of the bidentate ligands, the bound acetate ligand of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + either migrates within the same complex or into a different one, or is simply replaced. The reaction of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + (1) with 2,2′-bipyridine produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe) 2] (2), [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-bpy)] + (3), and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-bpy) 2] 2+ (4). Alternatively compound 2 can be prepared from the reaction of 1a with MeCO 2H–Et 3N, while compound 4 can be obtained from the reaction of 3 with bpy. The reaction of 1b with acetylacetone–Et 3N produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-acac)] (5) and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-acac) 2] (6). Compound 2 can also react with acetylacetone–Et 3N to produce 6. Surprisingly [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-quin) 2] (7) was obtained stereospecifically as the only one product from the reaction of 1b with 8-quinolinol–Et 3N. The structure of 7 has been established by X-ray crystallography and found to adopt a cis geometry. Further, the stereospecific reaction is probably caused by the second-sphere π–π face-to-face stacking interactions between the phenyl rings of dppm and the electron-deficient six-membered ring moiety of the bound quinolinate (i.e. the N-included six-membered ring) in 7. The presence of such interactions is indeed supported by an observed charge-transfer band in a UV–vis spectrum. 相似文献
9.
The bimetallic [Pt(NH 3) 4] 2[W(CN) 8][NO 3]·2H 2O is characterised by single-crystal X-ray diffraction [S.G. P2 1/ m(11), a=8.0418(7), b=19.122(2), c=9.0812(6) Å, Z=2]. All platinum centres have the square-plane D4h geometry with average dimensions Pt(1)–N 2.042(2) and Pt(2)–N 2.037(10) Å. The octacyanotungstate anion has the square-antiprismatic D4d configuration with average dimensions W(1)–C 2.164(13), C–N 1.140(12), W(1)–N 3.303(5) Å. The structure exhibits two different mutual orientations of Pt versus W units resulting in Pt(2)–W(1), W(1) * separations of 4.77(2), 4.55(2) * and Pt(1)–W(1) of 6.331(8) Å. A centrosymmetric structure reveals groups of two distinct columns: the first is formed by intercalated NO 3− between parallel [Pt(1)(NH 3) 4] 2+ planes and the second consists of [W(CN) 8] 3− interlayered by, parallel to square faces of W-antiprisms, [Pt(2)(NH 3) 4] 2+. The structure is stabilised through a three-dimensional hydrogen bond network via nitrogen atoms of cyanide ligands, hydrogen atoms of NH 3 ligands, water molecules and oxygen atoms of NO 3− counteranions. The vibrational pattern and the range of ν(CN) frequencies attributable to the electronic environment of W(V) and W(IV) are consistent with the ground state Pt(II)↔W(V) charge transfer. 相似文献
10.
The synthesis and reactivity of {(η 5-C 5H 4SiMe 3) 2Ti(CCSiMe 3) 2} MCl 2 (M = Fe: 3a; M = Co: 3b; M = Ni: 3c) is described. The complexes 3 are accessible by the reaction of (η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2 (1) with equimolar amounts of MCl 2 (2) (M = Fe, Co, Ni). 3a reacts with the organic chelat ligands 2,2′-dipyridyl (dipy) (4a) or 1,10-phenanthroline (phen) (4b) in THF at 25°C to afford in quantitative yields (η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2 (1) and [Fe(dipy) 2]Cl 2 (5a) or [Fe(phen) 2]Cl 2 (5b). 1/ n[Cu IHal] n (6) or 1/ n[Ag IHal] n (7) (Hal = Cl, Br) react with {(η 5 -C 5H 4SiMe 3) 2Ti(CCSiMe 3) 2}FeCl 2 (3a), by replacement of the FeCl 2 building block in 3a, to yield the compounds {(η 5-C 5H 4SiMe 3) 2Ti(C CSiMe 3) 2}Cu IHal (8) or {(η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2}Ag IHal (9) (Hal = Cl, Br), respectively. In 8 and 9 each of the two Me 3SiCC-units is η 2-coordinated to monomeric Cu I Hal or Ag IHal moieties. Compounds 8 and 9 can also be synthesized by the reaction of (η 5-C 5H 4SiMe 3) 2 Ti(CSiMe 3) 2 (1) with 1/ n[Cu IHal] n (6) or 1/ n [Ag IHal] n (7) in excellent yields. All new compounds have been characterized by analytical and spectroscopic data (IR, 1H-NMR, MS). The magnetic moments of compounds 3 were measured. 相似文献
11.
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
12.
The cationic diphenylphosphido-bridged compound [Ru 2(μ-PPh 2)(μ-OH) 2(η 6- p-cymene) 2][PF 6) (2) has been prepared by reaction of the tri-μ-hydroxo complex [Ru 2(μ-OH) 3(η- p-cymene) 2][PF 6] (1) with diphenylphosphine. Complex 2 eliminates water on reaction with protic acids, incorporating the conjugate base of the added acid as a bridging ligand. Formic acid, acetic acid, phenol, and aniline react with 2 to give the monosubstituted compounds [Ru 2(μ-PPh 2)(μ-OH)(μ-L)(η 6- p-cymene) 2]PF 6] (L = HCO 2, MeCO 2, OPh, or NHPH), whereas methanol, thiophenol, 1,2-benzenedithiol, hydrochloric acid and isopropanol afford the disubstituted derivatives [Ru 2(μ-PPh 2)(μ-L) 2(η 6- p-cymene) 2]PF 6] (L = OMe, SPh,
S 2C 6H 4, Cl, or H). 相似文献
13.
Reaction of [Pt 2(η 5-C 5Me 5) 2(η-Br) 3] 3+(Br −) 3 with C 5R 5H (R = H,Me) in the presence of AgBF 4 gives the first platinocenium dications, [Pt(η 5-C 5Me 5)(η 5-C 5R 5)] 2+(BF 4− ) 2. On electrochemical reduction, [pt(η 5-C 5Me 5) 2] 2+ yields [Pt(η 4-C 5Me 5H)(η 2-C 5Me 5)]+ BF 4−. kw]Cyclopentadienyl; Metallocenes; Platinum; Electrochemistry 相似文献
14.
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
15.
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
16.
Reaction of L {L = [24]aneS 8, [28]aneS 8} with two molar equivalents of [Cu(NCMe) 4]X (X − = ClO 4−, BF 4−, PF 6−) in MeCN affords the white binuclear copper(I) complexes [Cu 2(L)] 2+. A single crystal X-ray structure determination of [CU 2([24]aneS 8)](BF 4) 2 shows two tetrahedral copper(I) centres, each of which is coordinated to four thioether sulphur-donors, Cu---S(1) = 2.263(3), Cu---S(4) = 2.363(3), Cu---S(7) = 2.349(3), Cu---S(10) = 2.261(3) Å. The Cu … Cu distance is 5.172(3) Å. A single crystal X-ray structure determination Of [CU 2([28]aneS 8)](ClO 4) 2 shows that this complex also contain two tetrahedral copper(I) centres, each coordinated to four thioether sulphur-donors, Cu---S(1) = 2.278(5), Cu---S(4) = 2.333(5), Cu---S(8) = 2.328(5), CU---S(11) = 2.268(5) Å. The Cu … Cu distance of 6.454(3) Å is greater than in [CU 2([24]aneS 8)] 2+ , reflecting the greater cavity size in [CU 2([28]aneS 8)] 2+. Cyclic voltammetry of [CU 2([24]aneS 8)] 2+ and [CU 2([28]aneS 8)] 2+ at platinum electrodes in MeCN (0.1 M nBU 4NPF 6) shows irreversible oxidations at Epa, = +0.88 V, +0.92 V vs Fc/Fc +, respectively, at a scan rate of 200 mV s −1. Coulometric measurements in MeCN confirm these oxidations to be two-electron (one electron per copper) processes to give binuclear copper(II) species. Oxidation of the binuclear copper(I) precursors with H 2SO 4 or HNO 3 affords ESR-active copper(II) species which presumably incorporate SO 42− and NO 3− bridges. 相似文献
17.
[Co(η 2-CO 3)(NH 3) 4](NO 3)·0.5H 2O and [(NH 3) 3Co(μ-OH) 2(μ-CO 3)Co(NH 3) 3][NO 3] 2·H 2O were prepared by prolonged aerial oxidation of a solution of Co(NO 3) 2·6H 2O and ammonium carbonate in aqueous ammonia. The formation of these side products highlights the richness of the chemistry of these systems and the possibility of by products if methods are not strictly adhered to. The X-ray crystal structures of [Co(η 2-CO 3)(NH 3) 4][NO 3]·0.5H 2O and [(NH 3) 3Co(μ-OH) 2(μ-CO 3)Co(NH 3) 3][NO 3] 2·H 2O reveal a monomeric octahedral cobalt center with η 2-bound CO 32− in the former, while the latter consists of a dimeric array where the two cobalt centers are bridged by two OH − and one μ 2-CO 32− groups with three terminal NH 3 ligands for each Co center. In both complexes extensive hydrogen bonding interactions are evident. 相似文献
18.
Transamination reactions utilizing the compound mercuric bis(trimethylsilyl)amide, Hg{N(SiMe 3) 2} 2, in tetrahydrofuran (THF), and the metals Na, Mg, Ca, Sr, Ba and Al have been investigated. Thus the THF solvated compounds Na[N(SiMe 3) 2]·THF and M[N(SiMe 3) 2] 2·2THF, M = Mg, Ca, Sr and Ba (1–4), have been prepared. The X-ray crystal structures of 1 and the related manganese compound Mn[N(SiMe 3) 2] 2·2THF (5) are reported. Interaction of the silylamides, 2–4, with a range of crown ethers apparently proceeded with elimination of silylamine, (Me 3Si) 2NH, and novel ring opening of the crown ethers, generating species containing a donor alkoxide ligand with a vinyl ether function, presumably, ---O(CH 2CH 2O) nCH=CH 2 ( n = 3−5). The silylamides 2–4 were also cleanly converted to the corresponding alkoxides (from 1H NMR data) in reactions with stoichiometric quantities of 3-ethyl-3-pentanol. 相似文献
19.
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
20.
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
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