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二氯二茂锆与等当量的各种芳肟的钠盐在二氯甲烷中反应,得到10种二氯二茂锆取代衍生物,均为新化合物。这些化合物对水、空气和光敏感,稳定性差。对它们的合成及IR,^1HNMR进行了初步讨论。 相似文献
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近年来桥联二茂锆配合物的化学引起了金属有机化学家的兴趣,这是由于与非桥联二茂锆化合物相比,它们在结构上和反应性能上都有独特之处。文献中只报道了含 C、Si、Ge 和 O 的桥联二茂锆配合物的合成。 相似文献
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本文由二氯二茂锆和二氯二(甲基环戊二烯基)锆与二茂铁羧酸钠盐反应合成了六种二茂铁酰氧基茂锆配合物,R_2ZrClY:R=C_5H_5,Y=FcCOO(1),FcCH_2COO(2),FcCOCH_2CH_2COO(3);R=CH_3C_5H_4,Y=FcCOO(4),FcCH_2C0O(5),FcCOCH_2CH_2COO(6)(Fc=二茂铁基)。 相似文献
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由新孟基环戊二烯和三甲基硅基环戊二烯制备了两个前手性的二茂锆配合物。由它们与亲核试剂的反应,合成了一些新的,手性在锆原子上的锆配合物。^1HNMR和^1^3CNMR谱图表明,配体上的手性基团对锆原子上的取代反应有明显的手性诱导效果。 相似文献
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二茂锆杂环羧酸衍生物的合成陈宏明(北京医科大学药学院100083)应卫,周耀坤(兰州大学化学系730000)1961年NationalLeadCo.[1]首先以专利形式报导了一些二茂钛羧酸衍生物的合成,并发现这类化合物可作为烯烃的聚合催化剂。近几年又... 相似文献
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大取代茂锆配合物合成及分子内消除反应研究 总被引:1,自引:0,他引:1
通过6,6-二烷基富烯与2-MeOArLi进行加成反应, 得到含芳氧取代的环戊二烯基锂盐, 再与取代茂三氯化锆反应, 合成了不对称大位阻取代茂锆配合物RCpCpoZrCl2 [Cpo=2-MeOArCR1R2Cp, R1, R2=CH3, C2H5, (CH2)5, etc.], 所得的配合物均通过1H NMR, IR, MS和EA鉴定. 在此过程中发现该类配合物能进行分子内消除反应, 脱去苯甲醚得到烯基取代的二氯二茂锆配合物, 该反应为未见文献报道的新反应, 对该反应进行了研究. 相似文献
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本文研究了Cp_2ZrH_2与丙烯酸和Cp_2Zr(H)Cl与丙烯酸钠、巴豆酸钠的反应。产物由IR 1~H和~(13)CNMR、ESR谱、气相色谱以及化学方法分析鉴定。产物水解得到与底物相应的饱和酸.用~1H NMR方法考察了Cp_2ZrH_2与丙烯酸的反应过程,用IR方法考察了Cp_2Zr(H)Cl与丙烯酸钠的反应过程。实验结果表明,上面两种反应首先消除H_2或NaCl,形成锆氧健,然后碳碳双键还原生成二茂锆羧酸盐配合物,其中羧酸根离子与二茂锆桥式双齿配位。 相似文献
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A simple new route to access heterometallic alkoxo precursors for a wide range of materials is reported. This unique synthetic method comprises elimination of the cyclopentadienyl ring from Cp2MCl2 (M = Ti, Zr) as CpH in the presence of M'(OR)2 (M' = Ca, Mn; OR = OCH2CH2OCH3 or OEt) in an alcohol as a source of protons. In one-pot reactions, we have prepared four different compounds with Ti2Ca4(mu6-O), Cp2Zr2Ca4(mu4-Cl), Zr10Mn10(mu3-O) 14, and Cp3Ti2(mu-OEt)2 motifs. The compounds were characterized by single-crystal X-ray structural analysis and NMR spectroscopy. 相似文献
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Bai G Ma Q Roesky HW Vidovic D Herbst-Irmer R 《Chemical communications (Cambridge, England)》2003,(7):898-899
A new route for organic polyoxometallic clusters describes the first dumb-bell-like organic polyoxozirconium hydroxide [[(Cp*Zr)4(mu5-O)(mu3-O)2(mu-OH)4]2Zr(mu-O)4] x 2C7H8 (2; Cp* = C5Me5) involving the treatment of the Br?nsted acidic organozirconium hydroxide [(Cp*Zr)6(mu4-O)(mu-O)4(mu-OH)8] x 2C7H8 (1) with organozirconium compounds. 相似文献
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Liu FC Yang CC Chen SC Lee GH Peng SM 《Dalton transactions (Cambridge, England : 2003)》2008,(27):3599-3604
From the reactions of Cp*ZrCl(3) with 3 equiv. of LiBH(3)R (R = CH(3), Ph), the organotrihydroborate complexes, Cp*Zr(BH(3)CH(3))(3), 1, and Cp*Zr(BH(3)Ph)(3), 2, were isolated. One of the Zr-H-B bonding interactions in 2 could be described as an intermediate case between the bidentate and tridentate modes. Reactions of and Cp*Zr(BH(4))(3), 3, with Lewis acid B(C(6)F(5))(3) in diethyl ether produced the novel 14-electron ionic compounds [(micro(3)-O)(micro(2)-OC(2)H(5))(3){(Cp*Zr(OC(2)H(5)))(2)(BCH(3))}][HB(C(6)F(5))(3)], 4, and [(micro(3)-O)(micro(2)-OC(2)H(5))(3){(Cp*Zr(OC(2)H(5)))(2)(BOC(2)H(5))}][HB(C(6)F(5))(3)], 5, respectively. These two unique compounds resulted from a sequential cleavage of Zr-H-B bonds of 1 and 3 and C-O bonds of ether followed by the formation of O-B bonds. The solid state single crystal X-ray analyses revealed that both compounds have similar structures. A micro(3)-oxygen bridges two zirconiums and a boron atom. The latter three atoms are further connected by three micro(2)-bridging ethoxy groups giving rise to three four-membered metallacycles within the structure of each cation. 相似文献
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Sánchez-Nieves J Frutos LM Royo P Castaño O Herdtweck E Mosquera ME 《Inorganic chemistry》2010,49(22):10642-10648
Hydrolysis of [NbCp'Cl(4)] (Cp' = η(5)-C(5)H(4)SiMe(3)) with the water adduct H(2)O·B(C(6)F(5))(3) afforded the oxo-borane compound [NbCp'Cl(2){O·B(C(6)F(5))(3)}] (2a). This compound reacted with [MgBz(2)(THF)(2)] giving [NbCp'Bz(2){O·B(C(6)F(5))(3)}] (2b), whereas [NbCp'Me(2){O·B(C(6)F(5))(3)}] (2c) was obtained from the reaction of [NbCp'Me(4)] with H(2)O·B(C(6)F(5))(3). Addition of Al(C(6)F(5))(3) to solutions containing the oxo-borane compounds [MCp(R)X(2){O·B(C(6)F(5))(3)}] (M = Ta, Cp(R) = η(5)-C(5)Me(5) (Cp*), X = Cl 1a, Bz 1b, Me 1c; M = Nb, Cp(R) = Cp', X = Cl 2a) afforded the oxo-alane complexes [MCp(R)X(2){O·Al(C(6)F(5))(3)}] (M = Ta, Cp(R) = Cp*, X = Cl 3a, Bz 3b, Me 3c; M = Nb, Cp(R) = Cp', X = Cl 4a), releasing B(C(6)F(5))(3). Compound 3a was also obtained by addition of Al(C(6)F(5))(3) to the dinuclear μ-oxo compound [TaCp*Cl(2)(μ-O)](2), meanwhile addition of the water adduct H(2)O·Al(C(6)F(5))(3) to [TaCp*Me(4)] gave complex 3c. The structure of 2a and 3a was obtained by X-ray diffraction studies. Density functional theory (DFT) calculations were carried out to further understand these types of oxo compounds. 相似文献
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Mehdoui T Berthet JC Thuéry P Salmon L Rivière E Ephritikhine M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):6994-7006
Treatment of [Ce(Cp*)(2)I] or [U(Cp*)(2)I(py)] with 1 mol equivalent of bipy (Cp*=C(5)Me(5); bipy=2,2'-bipyridine) in THF gave the adducts [M(Cp*)(2)I(bipy)] (M=Ce (1 a), M=U (1 b)), which were transformed into [M(Cp*)(2)(bipy)] (M=Ce (2 a), M=U (2 b)) by Na(Hg) reduction. The crystal structures of 1 a and 1 b show, by comparing the U-N and Ce-N distances and the variations in the C-C and C-N bond lengths within the bidentate ligand, that the extent of donation of electron density into the LUMO of bipy is more important in the actinide than in the lanthanide compound. Reaction of [Ce(Cp*)(2)I] or [U(Cp*)(2)I(py)] with 1 mol equivalent of terpy (terpy=2,2':6',2'-terpyridine) in THF afforded the adducts [M(Cp*)(2)(terpy)]I (M=Ce (3 a), M=U (3 b)), which were reduced to the neutral complexes [M(Cp*)(2)(terpy)] (M=Ce (4 a), M=U (4 b)) by sodium amalgam. The complexes [M(Cp*)(2)(terpy)][M(Cp*)(2)I(2)] (M=Ce (5 a), M=U (5 b)) were prepared from a 2:1 mixture of [M(Cp*)(2)I] and terpy. The rapid and reversible electron-transfer reactions between 3 and 4 in solution were revealed by (1)H NMR spectroscopy. The spectrum of 5 b is identical to that of the 1:1 mixture of [U(Cp*)(2)I(py)] and 3 b, or [U(Cp*)(2)I(2)] and 4 b. The magnetic data for 3 and 4 are consistent with trivalent cerium and uranium species, with the formulation [M(III)(Cp*)(2)(terpy(*-))] for 4 a and 4 b, in which spins on the individual units are uncoupled at 300 K and antiferromagnetically coupled at low temperature. Comparison of the crystal structures of 3 b, 4 b, and 5 b with those of 3 a and the previously reported ytterbium complex [Yb(Cp*)(2)(terpy)] shows that the U-N distances are much shorter, by 0.2 A, than those expected from a purely ionic bonding model. This difference should reflect the presence of stronger electron transfer between the metal and the terpy ligand in the actinide compounds. This feature is also supported by the small but systematic structural variations within the terdentate ligands, which strongly suggest that the LUMO of terpy is more filled in the actinide than in the lanthanide complexes and that the canonical forms [U(IV)(Cp*)(2)(terpy(*-))]I and [U(IV)(Cp*)(2)(terpy(2-))] contribute significantly to the true structures of 3 b and 4 b, respectively. This assumption was confirmed by the reactions of complexes 3 and 4 with the H(.) and H(+) donor reagents Ph(3)SnH and NEt(3)HBPh(4), which led to clear differentiation of the cerium and uranium complexes. No reaction was observed between 3 a and Ph(3)SnH, while the uranium counterpart 3 b was transformed in pyridine into the uranium(IV) compound [U(Cp*)(2){NC(5)H(4)(py)(2)}]I (6), where NC(5)H(4)(py)(2) is the 2,6-dipyridyl(hydro-4-pyridyl) ligand. Complex 6 was further hydrogenated to [U(Cp*)(2){NC(5)H(8)(py)(2)}]I (7) by an excess of Ph(3)SnH in refluxing pyridine. Treatment of 4 a with NEt(3)HBPh(4) led to oxidation of the terpy(*-) ligand and formation of [Ce(Cp*)(2)(terpy)]BPh(4), whereas similar reaction with 4 b afforded [U(Cp*)(2){NC(5)H(4)(py)(2)}]BPh(4) (6'). The crystal structures of 6, 6' and 7 were determined. 相似文献
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The molybdenum nitrosyl complex Cp*Mo(NO)(CH2CMe3)(C6H5) reacts at room temperature via elimination of neopentane or benzene to form the transient species Cp*Mo(NO)(=CHCMe3) and Cp*Mo(NO)(eta2-C6H4). These reactive intermediates effect the intermolecular activation of hydrocarbon C-H bonds via the reverse of the transformations by which they are generated. Thermolysis of Cp*Mo(NO)(CH2CMe3)(C6H5) in pyridine yields the adducts Cp*Mo(NO)(=CHCMe3)(NC5H5) and Cp*Mo(NO)(eta2-C6H4)(NC5H5), and the benzyne complex has been characterized by X-ray diffraction. 相似文献
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Alvarez CS Bond AD Cave D Mosquera ME Harron EA Layfield RA McPartlin M Rawson JM Wood PT Wright DS 《Chemical communications (Cambridge, England)》2002,(24):2980-2981
The reactions of manganocene, Cp2Mn, with 2-aminopyridine (L1H) or 2-amino-3-bromo-5-methylpyridine (L2H) give the novel hexanuclear and octanuclear Mn(II) amido cage compounds [Cp2Mn3(L1)4]2 (1) and [Mn8(L2)12(mu 4-O)2] (2); magnetic measurements on which provide a rare insight into the magnetic properties of amido-bridged metal clusters. 相似文献
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Xie YP Yang J Ma JF Zhang LP Song SY Su ZM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(13):4093-4103
Reactions of Ph(3)SnOH or Ph3SnCl with aryl arsonic acids RAsO3H2, where R=C6H5 (1), 2-NH2C6H4 (2), 4-NH2C6H4 (3), 2-NO2C6H4 (4), 3-NO2C6H4 (5), 4-NO2C6H4 (6), 3-NO2-4-OHC6H3 (7), 2-ClC6H4 (8) and 2,4-Cl2C6H3 (9), gave 18 Sn-O cluster compounds. These compounds can be classified into four types: type A: [{(PhSn)3(RAsO3)3(mu3-O)(OH)(R'O)2}2Sn] (R=C6H5, 2-NH2C6H4, 4-NH2C6H4, 2-NO2C6H4, 3-NO2C6H4, 2-ClC6H4, 2,4-Cl2C6H3, and 3-NO2-4-OHC6H3; R'=Me or Et); type B: [{(PhSn)3(RAsO3)(2)(RAsO3H)(mu3-O)(R'O)2}2] (R=4-NO2C6H4, R'=Me); type C: [{(PhSn)3(RAsO3)3(mu3-O)(R'O)3}2Sn] (R=2,4-Cl2C6H3, R'=Me); type D: [{Sn3Cl3(mu3-O)(R'O)3}(2)(RAsO3)4] (R=2-NO2C6H4 and 4-NO2-C6H4; R'=Me or Et). Structures of types A and B contain [Sn3(mu3-O)(mu2-OR')2] building blocks, while in types C and D the stannoxane cores are built from two [Sn3(mu3-O)(mu2-OR')3] building blocks. The reactions proceeded with partial or complete dearylation of the triphenyltin precursor. These various structural forms are realized by subtle changes in the nature of the organotin precursors and aryl arsonic acids. The syntheses, structures, and structural interrelationship of these organostannoxanes are discussed. 相似文献