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1.
4,4′-二溴联苯与n-BuLi反应得到对-联苯基二锂,再与四甲基环戊烯酮进行羰基加成,酸催化脱水,一步得到对-联苯基桥连四甲基环戊二烯配体4-(C 5Me 4H)C 6H 4-C 6H 4(C 5Me 4H)-4(1).配体1相继与n-BuLi和ZrCl 4反应得到相应的联苯基桥连双(单茂三氯化锆)4-(C 5Me 4ZrCl 3)C 6H 4-C 6H 4(C 5Me 4ZrCl 3)-4,不经分离直接与环戊二烯基锂或茚基锂反应得到相应的双核锆化合物4-(C 5MeZrCl 2Cp′)C 6H 4-C 6H 4·(C 5Me 4ZrCl 2Cp′)-4[Cp′=C 5H 5(2),C 9H 7(3)].研究了在MAO(MethylAluminoxane)助催化下,化合物2和3对乙烯聚合的催化性能.化合物2和3都显示了非常高的催化活性,并在较高的温度下达到最高活性. 相似文献
2.
139La-NMR chemical shifts were measured for several anionic complexes of formulae Li(C 4H 8O 2) 3/2 [La(ν 3-C 3H 5) 4], [Li(C 4H 8O 2) 2][Cp′ nLa(ν 3-C 3]H 5) 4−n] (Cp′ = Cp(ν 5-C 5H 5); n = 1, 2 and Cp′ = Cp * (ν 5-C 5Me5); N = 1) and Li[R nLa(ν 3-C 3H 4) 4− n] (R = N(SiMe 3) 2; n = 1, 2 and R = CCsIMe 3; n = 4), as well as for neutral compounds for formulae La(ν 3-C 3H 5) 3L n (L = (C 4H 8O 2) 1.5, (HMPT) 2, TMED), Cp′ nLa(ν 3-C 3H 5) 3−n (Cp′= Cp(ν 5-Cp 5H 5), Cp *(ν 5-C 5Me 5); n = 1, 2) and La(ν 3-C 3H 2) 2X(THF) 2 X = Cl, Br, I). Typical ranges of the 139La-NMR chemical shifts were found for the different types of complex independent of number and kind of organyl groups directly bonded to lanthanum. Zusammenfassung139La-NMR-Spektroskopie wurde an einer Reihe anionischer Allyllanthanat(III)-Komplexe der Zusammensetzung
]- [La)ν3-C3H5)4, [Li(C4H8)2][Cp′nLa(ν3-C3H5)4−n(Cp′ = Cp(ν5-C5H5); n = 1, 2 und Cp′ = Cp * (ν5-C5Me5); N = 1) und Li[RnLa(ν3-C3H5)4−n (R = B(SiMe3)2; n = 1, 2 und R = CCSiMe3; n = 4 sowie neutraler Allyllanthan(III)-Komplexe der Zusammensetzung La(ν3-C3H5)3Ln (Ln = (C4H8O2)1.5, (HMPT)2, TMED), Cp′n, La(ν3-C3H5)3−n (Cp′ = Cp(ν5-C5H5), Cp * (ν5- Cp5Me5); n = 1, 2) und La(ν3-Cp3H5)2X(THF)2 (X = Cl, Br, I) durchgefürt. In Abhängikeit von der Anzahl und der Art der am Lanthan gebundenen Gruppen wurden für die verschieden Komplextypen charakteristische Resonanzbereiche ermittelt. 相似文献
3.
The mono- and bis-cyclopentadienyl compounds 1-(Cp″)-4-(CH 3)C 6H 4 (1) and 1, 4-(Cp″) 2C 6H 4 (2) (Cp″ = 3,4-dimethylcyclopenta-1,3-diene-1-yl) have been synthesized. The reactions of the lithium salts of 1 and 2 with CpZrCl 3 · dme (dme = dimethoxyethane) and Cp*ZrCl 3(CP* = C 5(CH 3) 5) yielded the mono- and bi-nuclear bridged zirconocenes 1-(Cp″ZrCpCl 2)-4-(CH 3)C 6H 4 (3), 1,4-(Cp″ZrCpCl 2) 2C 6H 4 (4) and 1,4-(Cp″ZrCp*Cl 2) 2C 6H 4 (5). When activated with methylaluminoxane (MAO), the mono- and bi-nuclear zirconocenes 3 and 4 catalyse the polymerization of propene. The influence of the catalyst composition on the polymerization kinetics and molecular weight is discussed. 相似文献
4.
The new chloro(cyclopentadienyl)silanes Cp′SiH yCl 3−y (Cp′=Me 4EtC 5, y=1: 1; Cp′=Me 4C 5H, y=1: 2; y=0: 3; Cp′=Me 3C 5H 2, y=1: 4 and pentachloro(cyclopentadienyl)disilanes Cp′Si 2Cl 5 (Cp′=Me 5C 5 5, Me 4EtC 5 6, Me 4C 5H 7, Me 3C 5H 2 8, Me 3SiC 5H 4 9) are synthesized in good yields via metathesis reactions. Treatment of 1–9 with LiAlH 4 leads under Cl–H exchange to the hydridosilyl compounds Cp′SiH 3 (Cp′=Me 4EtC 5 10, Me 4C 5H 11, Me 3C 5H 2 12) and to the hydridodisilanyl compounds Cp′Si 2H 5 (Cp′=Me 5C 5 13, Me 4EtC 5 14, Me 4C 5H 15, Me 3C 5H 2 16, Me 3SiC 5H 4 17). Complexes 1–17 are characterized by 1H, 13C, and 29Si-NMR spectroscopy, IR spectroscopy, mass spectrometry and CH-analysis. The structures of 6, 7 and 9 are determined by single-crystal X-ray diffraction analysis. Pyrolysis studies of the cyclopentadienylsilanes 10–12 and disilanes 13–17 show their suitability as precursors in the MOCVD process. 相似文献
5.
Effects of substituents on cyclopentadienyl group for homopolymerization of ethylene, 1-hexene, and for ethylene/1-hexene copolymerization using a series of nonbridged (cyclopentadienyl)(ketimide)titanium complexes of the type, Cp′TiCl 2(N=C tBu 2) [Cp′ = Cp (1), tBuC 5H 4 (2), C 5Me 5 (Cp *, 3), and indenyl (4)] have been explored in the presence of methylaluminoxane (MAO) cocatalyst. Complexes 1–3 showed the similar catalytic activities for ethylene polymerization although the activity by 4 was somewhat low, whereas the activity for 1-hexene polymerization increased in the order 1 > 4 2 > 3. These complexes showed significant activities for ethylene/1-hexene copolymerization affording high molecular weight poly(ethylene- co-1-hexene)s with unimodal molecular weight distributions, and the activity increased in the order: 4 > 1 2, 3. The rErH values in the polymerization by 1–3 at 40 °C were 0.35–0.52 which clearly indicate that the 1-hexene incorporation in the copolymerization did not proceed in a random manner. The rE values by 1–3 were 6.0–6.4 and the values were independent upon the cyclopentadienyl fragment employed; the rE values by 4 at 40 °C were 10.2–10.9 which were close to those by ansa-metallocene complex catalysts. These values were influenced by the polymerization temperature, and the 1-hexene incorporation by 1–4 became inefficient at higher temperature, although the observed activities especially by 1, 4 were highly remarkable. 相似文献
6.
The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C 5Me 4CH 2PMe 2)], where M=Li + (1), Na + (2), or K + (3), and [Li(C 5H 4CR′ 2PMe 2)], where R′ 2=Me 2 (4), or (CH 2) 5 (5), [HC 5Me 4CH 2PMe 2H]X, where X −=Cl − (6) or PF 6− (7) and [HC 5Me 4CH 2PMe 2] (8), are described. They have been used to prepare new metallocene compounds, of which representative examples are [Fe(η-C 5R 4CR′ 2PMe 2) 2], where R=Me, R′=H (9); R=H and R′ 2=Me 2 (10), or (CH 2) 5 (11), [Fe(η-C 5H 4CMe 2PMe 3) 2]I 2 (12), [Fe{η-C 5Me 4CH 2P(O)Me 2} 2] (13), [Zr(η-C 5R 4CR′ 2PMe 2) 2Cl 2], where R=H, R′=Me (14), or R=Me, R′=H (15), [Hf(η-C 5H 4CMe 2PMe 2) 2]Cl 2] (16), [Zr(η-C 5H 4CMe 2PMe 2) 2Me 2] (17), {[Zr(η-C 5Me 4CH 2PMe 2) 2]Cl}{(C 6F 5) 3BClB(C 6F 5) 3} (18), [Zr{(η-C 5Me 4CH 2PMe 2) 2Cl 2}PtI 2] (19), [Mn(η-C 5Me 4CH 2PMe 2) 2] (20), [Mn{(η-C 5Me 4CH 2PMe 2B(C 6F 5) 3} 2] (21), [Pb(η-C 5H 4CMe 2PMe 2) 2] (23), [Sn(η-C 5H 4CMe 2PMe 2) 2] (24), [Pb{η-C 5H 4CMe 2PMe 2B(C 6F 5) 3} 2] (25), [Pb(η-C 5H 4CMe 2PMe 2) 2PtI 2] (26), [Rh(η-C 5Me 4CH 2PMe 2)(C 2H 4)] 29, [M(η,κ P-C 5Me 4CH 2PMe 2)I 2], where M=Rh (30), or Ir, (31). 相似文献
7.
A series of silylene-linked cyclopentadienyl-phosphido rare earth alkyl and hydride complexes of type Me 2Si(C 5Me 4)(PR′)LnR (Ln=Y, Yb, Lu; R′=Ph, Cy, C 6H 2tBu 3-2,4,6; R=CH 2SiMe 3, H) have been synthesized and structurally characterized, and their activity in ethylene polymerization and olefin hydrosilylation has been studied. These complexes represent the first examples of rare earth alkyl and hydride complexes bearing cyclopentadienyl-phosphido ligands, which are in sharp contrast both structurally and chemically with the analogous cyclopentadienyl-amido and metallocene complexes. 相似文献
8.
The reaction of the metallocene dichlorides Cp 2MCl 2 (Cp = η 5-C 5H 5; M = Ti, Zr, Hf, Mo, W) and Cp 2′TiCl 2 (Cp′ = η 5-C 5H 4CH 3) with equimolar amounts of dilithium-benzene- o-diselenolate, 1,2-(LiSe) 2C 6H 4, gives the chelate complexes Cp 2M(Se 2C 6H 4) (M = Ti (I), Zr (II), Hf (III), Mo (IV), W (V)) and Cp 2′Ti(Se 2C 6H 4) (VI). CpTiCl 3 reacts with 1,2-(LiSe) 2C 6H 4 to give CpTiCl(Se 2C 6H 4) (VII). The ring inversion activation parameters for I–VI can be determined by means of temperature-dependent 1H NMR spectroscopy in solution. The fragmentation behaviour of I–VII in the mass spectrometer has been investigated by pursuing metastable transitions, using linked-scan techniques. 相似文献
9.
Cp 2MoH 2 reacts with methyl acrylate in the presence of acetylenes (L = C 2H 2, C 2Me 2, HCC tBu, HCCSiMe 3, C 2(SiMe 3) 2, HCCCH 2OMe, HCCCH 2NMe 2) to form acetylene complexes Cp 2Mo(L) 5. Protonation takes place with CF 3CO 2H at −80°C to give short-lived cations [Cp 2MoH(L) + (8) (L = C 2Me 2, HCCSiMe 3, C 2(SiMe 3) 2). The structure of [Cp 2MoH{η 2-C 2(SiMe 3) 2}]PF 6(9) was determined by an X-ray diffraction study. 相似文献
10.
A series of luminescent rhenium(I) monoynyl complexes, [Re(N---N)(CO) 3(CC---R)] (N---N=bpy, tBu 2bpy; R=C 6H 5, C 6H 4---Cl-4, C 6H 4---OCH 3-4, C 6H 4---C 8H 17-4, C 6H 4---C 6H 5, C 8H 17, C 4H 3S, C 4H 2S---C 4H 3S, C 5H 4N), together with their homo- and hetero-metallic binuclear complexes, {Re(N---N)(CO) 3(CC---C 5H 4N)[M]} (N---N=bpy, tBu 2bpy; [M]=[Re{(CF 3) 2-bpy}(CO) 3]ClO 4, [Re(NO 2-phen)(CO) 3]ClO 4, W(CO) 5) have been synthesized and their electrochemical and photoluminescence behaviors determined. The structural characterization and electronic structures of selected complexes have also been studied. The luminescence origin of the rhenium(I) alkynyl complexes has been assigned as derived states of a [dπ(Re)→π*(N---N)] metal-to-ligand charge transfer (MLCT) origin mixed with a [π(CCR)→π*(N---N)] ligand-to-ligand charge transfer (LLCT) character. The assignments are further supported by extended Hückel molecular orbital (EHMO) calculations, which show that the LUMO mainly consists of π*(N---N) character while the HOMO is dominated by the antibonding character of the Re---CCR moiety resulted from the overlap of the dπ(Re) and π(CCR) orbitals. 相似文献
11.
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
12.
The synthesis of the new (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,3-(C 6H 4X) ( m-2a/2b; X=F/Br) and (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4I) (2c) complexes, as well as the solid-state structure of the known (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4F) (2a) complex are described. The catalytic coupling reactions of the bromo complexes with various alkynes were next investigated. Starting from the known (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4Br) complex (2b), the synthesis of the (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4)---CC---H complex (6d) and of the corresponding silyl-protected precursors (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4)CC---SiR 3 (6b/6c; R= iPr/Me) are reported. By use of lithium---bromine exchange reactions on 2b, the silyl- (7a; E=Si; R=Me) and tin- (7b–7d; E=Sn; R=Me, Bu, Ph) substituted analogues (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4)ER 3 are also isolated. The spectroscopic and electrochemical characterisations of all these new Fe(II)/Fe(III) redox-active building blocks are presented and the electronic substituent parameters for the “(η 2-dppe)(η 5-C 5Me 5)Fe---CC” group are determined by means of 19F-NMR. 相似文献
13.
Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH 3) 2N-C 9H 6) 2ZrCl 2, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH 3) 2Si(2-(CH 3) 2N-C 9H 5) 2ZrCl 2, were prepared by reaction of the corresponding ligand lithium salts with ZrCl 4 in toluene. Diffractometric structure determinations reveal C 2-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH 3) 2Si(2-(CH 3) 2N-C 9H 5) 2ZrCl 2 catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me 2Si-bridged bis(indenyl)ZrCl 2 complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species. 相似文献
14.
Treatment of the dimer complex [C 5Me 5 (CO) 2 Ru] 2 (1) with HBF 4 in CH 2Cl 2 at room temperature yields the hydrido-bridged dinuclear complex [(C 5Me 5) 2Ru 2(CO) 4H]BF 4 (2), and after refluxing in propionic anhydride [C 5Me 5(CO) 3Ru]BF 4 (5) is obtained, UV-irradiation of 1 in the presence of H 2CHal 2 (Hal = Cl, I) or trimethylphosphine leads to the formation of C 5Me 5(CO) 2Ru-Hal (3a, 3b) or C 5Me 5(CO)(Me 3P)RuH (4) respectively. Exchange reactions of 3a, 3b with LiAlH 4, NaOMe and Me 3 P give the complexes C 5Me 5(CO) 2RuX (6a,6b) (X=H, OMe), C 5Me 5(CO)(Me 3P)Ru-Hal (7a,7b) (Hal = Cl, I) and C 5Me 5(Me 3P) 2RuI (8). The interaction of 3b or 5 with Me 3P=CH 2 leads to the formation of the ylide complex [C 5Me 5(CO)(Me 3P)-RuCH 2PMe 3)Cl (9) or the rutheniumacyl-ylide C 5Me 5(CO) 2RuC(O)CH=PMe 3 (10). 4 reacts with Me 3P=CH 2 to give C 5Me 5(CO)(Me 3P)RuMe (11) and Me 3P via the intermediate formation of the phosphonium salt Me 4P[Ru(CO) (Me 3P)-C 5Me 5]. 相似文献
15.
In order to understand the nature of the putative cationic 12-electron species [M(η 5:η 1-C 5R 4SiMe 2NR′)R″] + of titanium catalysts supported by a linked amido-cyclopentadienyl ligand, several derivatives with different cyclopentadienyl C 5R 4 and amido substituents R′ were studied systematically. The use of tridentate variants (C 5R 4SiMe 2NCH 2CH 2X) 2− (C 5R 4=C 5Me 4, C 5H 4, C 5H 3tBu; X=OMe, SMe, NMe 2) allowed the NMR spectroscopic observation of the titanium benzyl cations [Ti(η 5:η 1-C 5Me 4SiMe 2NCH 2CH 2X)(CH 2Ph)] +. Isoelectronic neutral rare earth metal complexes [Ln(η 5:η 1-C 5R 4SiMe 2NR′)R″] can be expected to be active for polymerization. To arrive at neutral 12-electron hydride and alkyl species of the rare earth metals, we employed a lanthanide tris(alkyl) complex [Ln(CH 2SiMe 3) 3(THF) 2] (Ln=Y, Lu, Yb, Er, Tb), which allows the facile synthesis of the linked amido-cyclopentadienyl complex [Ln(η 5:η 1-C 5Me 4SiMe 2NCMe 3)(CH 2SiMe 3)(THF)]. Hydrogenolysis of the linked amido-cyclopentadienyl alkyl complex leads to the dimeric hydrido complex [Ln(η 5:η 1-C 5Me 4SiMe 2NCMe 3)(THF)(μ-H)] 2. These complexes are single-site, single-component catalysts for the polymerization of ethylene and a variety of polar monomers such as acrylates and acrylonitrile. Nonpolar monomers such as -olefins and styrene, in contrast, give isolable mono-insertion products which allow detailed studies of the initiation process. 相似文献
16.
The title compounds react with unidentate ligands, L, containing either phosphorus or arsenic donor atoms to yield the corresponding compounds of the type Ru(η 5---C 5Me 4Et)(CO)LX; with didentate phosphorus donor ligands the major species formed is the bridged complex {Ru(η 5---C 5Me 4Et)(CO)X} 2{Ph 2P(CH 2) nPPh 2} n = 1, X = Br; n = 2, X = Cl). In contrast, unidentate ligands containing nitrogen donor atoms such as pyridine did not react with Ru(η 5---C 5Me 4Et)(CO) 2Cl although reaction with 1,10-phenanthroline or diethylenetriamine yielded the ionic products [Ru(η 5---C 5Me 4Et)(CO)L] +Cl − (L = phen or (NH 2CH 2CH 2) 2NH). Reaction of Ru(η 5---C 5Me 4Et)(CO) 2Br with AgOAc yielded the corresponding acetato complex Ru(η 5---C 5Me 4Et)(CO) 20Ac. Ru(η 5--- C 5Me 4Et)(CO) 2X reacts with AgY (Y = BF 4 or PF 6) in either acetone or dichloromethane to give the useful solvent intermediates [Ru(η 5---C 5Me 4Et)(CO) 2(solvent)] +Y −, which readily react with ligands L to yield ionic derivatives of the type [Ru(η 5---C 5Me 4Et)(CO) 2L] +Y − (where L = CO, NCMe, py, C 2H 4 or MeO 2CCCCO 2Me). 相似文献
17.
Neutral salicylaldiminato Ni(II) complexes bearing a single N-heterocyclic carbene (NHC) ligand [3,5- tBu 2-2-(O)C 6H 2CHNAr]Ni(C{RNCHCHN iPr})Ph [Ar = 2,6- iPr 2C 6H 3, R = Bn (1); Ar = 2,6- iPr 2C 6H 3, R = iPr (2)], have been synthesized via a one-pot procedure in high yield. The X-ray structure analysis reveals that both of 1 and 2 adopt distorted square-planar coordination geometry and NHC carbon (C carbene) is trans to the ketimine nitrogen. Preliminary study indicates that complex 1 is inert toward the insertion of ethylene, however, it can catalyze the dimerization of ethylene in the presence of modified methylaluminoxane (MMAO) with a moderate activity of 3.05 × 10 4 g(mol Ni) −1 h −1 atm −1 in a highly selective fashion. 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.
Irradiation of Cp 2* Nb(η 2---S 2)H (Cp * = C 5Me 5) 1a in the presence of Fe(CO) 5 gives the CO-free complex [Cp 2*NbS 2] 2Fe 2a. The core of 2a contains an FeS 4 tetrahedron which is ligated by two niobocene ligands as shown by X-ray diffraction analysis. In the reaction of 1a or Cp 2xNb(η 2---S 2)H (CP x = C 5Me 4Et) 1b with Co 2(CO) 8, compounds 3a and 3b of the same type are formed. Electrochemical studies of 2a and 3a,b show that they undergo three reversible 1e − steps. The oxidation of 3b exerts a considerable influence on its absorption spectrum. A qualitative EHMO analysis is in agreement with a strong delocalisation of electron density over the whole NbS 2MS 2Nb system. 相似文献
20.
Reaction of R---N=C=N---R (R= p-Me-C 6H 4) and R---P==C=P---R (R=2,4,6- tBu 3C 6H 2) with the di-iron aminocarbene complex [Fe 2(CO) 7{1μ-C(Ph)C(NEt 2)}] (1c) gave corresponding complexes [Fe 2(CO) 6{C(Ph)C(NEt 2)C(NC 6H 4Me)N (C 6H 4Me)}] (2) and [Fe 2(CO) 6{C(Ph)C(NEt 2)C(PC 6H 2tBu 3)P(C 6H 2tBu 3)}] (4), resulting from a coupling reaction with carbon-carbon bond formation. [Fe 2(CO) 5(CNC 6H 4Me){C(Ph)C(NEt 2)N(C 6H 4Me)}], complex 3, obtained in the reaction with R---N=C=N---R, resulted from C=N bond rupture insertion of a nitrene fragment into the Fe=C bond. Complexes 2–4 were characterized by X-ray diffraction. The different geornetries of complexes 2 and 4 are discussed. The formation of these complexes may be explained by cycloaddition on the Fe =C metal-carbene bond. 相似文献
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