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1.
Pradeep Mathur Vidya D. Avasare Shaikh M. Mobin 《Journal of organometallic chemistry》2004,689(7):1325-1327
Molybdenum dithiopropiolato complexes, [(η5-C5R4R′)Mo(CO)2(η2-S2CCCPh)] (R=H, R′=Me 1a, R=R′=H 1b; R=R′=Me 1c) react with trimethylamine-N-oxide (TMNO · 2H2O) under mild thermolysis to form 5-phenyl-1,2-dithiole-3-thione (2). The reaction proceeds through the formation of the oxo-complexes, [(η5-C5R4R′)Mo(O)(η3-S2CCCPh)] (R=H, R′=Me 3a, R=R′=H 3b; R=R′=Me 3c). Direct reaction of 3a-c with TMNO · 2H2O under thermolysis also results in formation of 2. 相似文献
2.
The synthesis and the characterization of some new aluminum complexes with bidentate 2-pyrazol-1-yl-ethenolate ligands are described. 2-(3,5-Disubstituted pyrazol-1-yl)-1-phenylethanones, 1-PhC(O)CH2-3,5-R2C3HN2 (1a, R = Me; 1b, R = But), were prepared by solventless reaction of 3,5-dimethyl pyrazole or 3,5-di-tert-butyl pyrazole with PhC(O)CH2Br. Reaction of 1a or 1b with (R1 = Me, Et) yielded N,O-chelate alkylaluminum complexes (2a, R = R1 = Me; 2b, R = But, R1 = Me; 2c, R = Me, R1 = Et). Compound 1a was readily lithiated with LiBun in thf or toluene to give lithiated species 3. Treatment of 3 with 0.5 equiv of MeAlCl2 or AlCl3 yielded five-coordinated aluminum complexes [XAl(OC(Ph)CH{(3,5-Me2C3HN2)-1})2] (4, X = Me; 5, X = Cl). Reaction of 5 with an equiv of LiHBEt3 generated [Al(OC(Ph)CH{(3,5-Me2C3HN2)-1})3] (6). Complex 6 was also obtained by reaction of 3 with 1/3 equiv of AlCl3. Treatment of 5 with 2 equiv of AlMe3 yielded complex 2a, whereas with an equiv of AlMe3 afforded a mixture of 2a and [Me(Cl)AlOC(Ph)CH{(3,5-Me2C3HN2)-1}] (7). Compounds 1a, 1b, 2a-2c and 4-6 were characterized by elemental analyses, NMR and IR (for 1a and 1b) spectroscopy. The structures of complexes 2a and 5 were determined by single crystal X-ray diffraction techniques. Both 2a and 5 are monomeric in the solid state. The coordination geometries of the aluminum atoms are a distorted tetrahedron for 2a or a distorted trigonal bipyramid for 5. 相似文献
3.
Vincenzo G Albano Fabio Marchetti Stefano Zacchini 《Journal of organometallic chemistry》2004,689(3):528-538
Terminal alkynes (HCCR′) (R′=COOMe, CH2OH) insert into the metal-carbyne bond of the diiron complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(NCMe)(Cp)2][SO3CF3] (R=Xyl, 1a; CH2Ph, 1b; Me, 1c; Xyl=2,6-Me2C6H3), affording the corresponding μ-vinyliminium complexes [Fe2{μ-σ:η3-C(R′)CHCN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Xyl, R′=COOMe, 2; R=CH2Ph, R′=COOMe, 3; R=Me, R′=COOMe, 4; R=Xyl, R′=CH2OH, 5; R=Me, R′=CH2OH, 6). The insertion is regiospecific and C-C bond formation selectively occurs between the carbyne carbon and the CH moiety of the alkyne. Disubstituted alkynes (R′CCR′) also insert into the metal-carbyne bond leading to the formation of [Fe2{μ-σ:η3-C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R′=Me, R=Xyl, 8; R′=Et, R=Xyl, 9; R′=COOMe, R=Xyl, 10; R′=COOMe, R=CH2Ph, 11; R′=COOMe, R=Me, 12). Complexes 2, 3, 5, 8, 9 and 11, in which the iminium nitrogen is unsymmetrically substituted, give rise to E and/or Z isomers. When iminium substituents are Me and Xyl, the NMR and structural investigations (X-ray structure analysis of 2 and 8) indicate that complexes obtained from terminal alkynes preferentially adopt the E configuration, whereas those derived from internal alkynes are exclusively Z. In complexes 8 and 9, trans and cis isomers have been observed, by NMR spectroscopy, and the structures of trans-8 and cis-8 have been determined by X-ray diffraction studies. Trans to cis isomerization occurs upon heating in THF at reflux temperature. In contrast to the case of HCCR′, the insertion of 2-hexyne is not regiospecific: both [Fe2{μ-σ:η3-C(CH2CH2CH3)C(Me)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Xyl, 13; R=Me, 15) and [Fe2{μ-σ:η3-C(Me)C(CH2CH2CH3)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Xyl, 14, R=Me, 16) are obtained and these compounds are present in solution as a mixture of cis and trans isomers, with predominance of the former. 相似文献
4.
Nicolas Bréfuel Isabelle Vang Sergiu Shova Françoise Dahan Jean-Pierre Costes Jean-Pierre Tuchagues 《Polyhedron》2007
The synthesis and characterization of new symmetrical FeII complexes, [FeLA(NCS)2] (1), and [FeLBx(NCS)2] (2–4), are reported (LA is the tetradentate Schiff base N,N′-bis(1-pyridin-2-ylethylidene)-2,2-dimethylpropane-1,3-diamine, and LBx stands for the family of tetradentate Schiff bases N,N′-bis[(2-R-1H-imidazol-4-yl)methylene]-2,2-dimethylpropane-1,3-diamine, with: R = H for LB1 in 2, R = Me for LB2 in 3, and R = Ph for LB3 in 4). Single-crystal X-ray structures have been determined for 1 (low-spin state at 293 K), 2 (high-spin (HS) state at 200 K), and 3 (HS state at 180 K). These complexes remain in the same spin-state over the whole temperature range [80–400 K]. The dissymmetrical tetradentate Schiff base ligands LCx, N-[(2-R2-1H-imidazol-4-yl)methylene]-N′-(1-pyridin-2-ylethylidene)-2,2-R1-propane-1,3-diamine (R1 = H, Me; R2 = H, Me, Ph), containing both pyridine and imidazole rings were obtained as their [FeLCx(NCS)2] complexes, 5–10, through reaction of the isolated aminal type ligands 2-methyl-2-pyridin-2-ylhexahydropyrimidine (R1 = H, 5–7) or 2,5,5-trimethyl-2-pyridin-2-ylhexahydropyrimidine (R1 = Me, 8–10) with imidazole-4-carboxaldehyde (R2 = H: 5, 8), 2-methylimidazole-4-carboxaldehyde (R2 = Me: 6, 9), and 2-phenyl-imidazole-4-carboxaldehyde (R2 = Ph: 7, 10) in the presence of iron(II) thiocyanate. Together with the single-crystal X-ray structures of 7 and 9, variable-temperature magnetic susceptibility and Mössbauer studies of 5–10 showed that it is possible to tune the spin crossover properties in the [FeLCx(NCS)2] series by changing the 2-imidazole and/or C2-propylene susbtituent of LCx. 相似文献
5.
The violet ruthenium complex [(η5-C5Me5)Ru(η5-C3B2Me4R1)] (2a, R1 = Me) reacts with terminal alkynes R2CCH to give yellow 4-borataborepine compounds [(η5-C5Me5)Ru{η7-(MeC)3(R1B)2(R2C2H)}] (4c, R1 = Me, R2 = Ph; 4d, R1 = Me, R2 = SiMe3; 4e, R1 = Me, R2 = H). The insertion of alkynes into the folded C3B2 heterocycle of 2a causes some steric hindrance, which yields with elimination of the distant boranediyl group the corresponding boratabenzene complexes 5 as byproducts. The analogous reactions with internal alkynes R2CCR2 proceed slowly and afford predominantly the boratabenzene complexes [(η5-C5Me5)Ru{η6-(MeC)3(MeB)(R2C)2}] (5f, R2 = Et, 5g, R2 = p-tolyl), respectively. In the latter case, three byproducts are formed: methylboronic acid and 1,2,3,4-tetra-p-tolyl-1,3-butadiene (9) due to hydrolysis of the postulated 2,3,4,5-tetra-p-tolyl-1-methylborole (10) and unexpectedly, the cationic triple-decker complex [{(η5-C5Me5)Ru}2{μ,η7-(MeC)3(MeB)2(CH)2}]Cl (11) having two separated CH groups. The new compounds were characterized by NMR, MS, and single-crystal X-ray studies of 4c, 5f, 9 and 11. 相似文献
6.
Eight new organotin (IV) carboxylates, (R3Sn)4(nap)4 (R = Me 1, n-Bu 2), [(R3Sn) (nap)]n (R = Ph 3, PhCH24), (R2Sn) (nap)2 (R = n-Bu 5, Ph 6, PhCH27) and {[R2Sn(nap)]2O}2 (R = Me 8) (nap = (S)-(+)-6-methoxy-α-methyl-2-naphthaleneaceto anion) have been synthesized. All of the complexes have been characterized by elemental analysis, FT-IR, NMR (1H, 13C and 119Sn) spectra. Among these complexes, complexes 1, 3, 5 and 8 were also characterized by X-ray crystallography diffraction analysis, and the data of X-ray crystallography diffraction indicated that complexes 1, 3 and 5 are new chiral organotin (IV) carboxylates complexes. The structural analyses show that complex 1 has a tetranuclear Sn4O8 macrocycle structure, complex 3 has a 1D spring-like chiral helical chain with a columnar channel, complex 5 possesses a dimer structure, and complex 8 has a supramolecular chainlike ladder structure through weak intermolecular non-covalent O…O interactions. 相似文献
7.
A series of organotin(IV) complexes with O,O-diethyl phosphoric acid (L1H) and O,O-diisopropyl phosphoric acid (L2H) of the types: [R3Sn · L]n (L = L1, R = Ph 1, R = PhCH22, R = Me 3, R = Bu 4; L = L2, R = Ph 9, R = PhCH210, R = Me 11, R = Bu 12), [R2Cl Sn · L]n (L = L1, R = Me 5, R = Ph 6, R = PhCH27, R = Bu 8; L = L2, R = Me 13, R = Ph 14, R = PhCH215, R = Bu 16), have been synthesized. All complexes were characterized by elemental analysis, TGA, IR and NMR (1H, 13C, 31P and 119Sn) spectroscopy analysis. Among them, complexes 1, 2, 3, 5, 8, 9 and 11 have been characterized by X-ray crystallography diffraction analysis. In the crystalline state, the complexes adopt infinite 1D infinite chain structures which are generated by the bidentate bridging phosphonate ligands and the five-coordinated tin centers. 相似文献
8.
9.
Kirill V. Zaitsev Yuri F. Oprunenko Judith A.K. Howard Galina S. Zaitseva 《Journal of organometallic chemistry》2008,693(1):173-179
Novel substituted 2-[(2-hydroxyethyl)]aminophenols, MeN(CHR1CR2R3OH)(C6H4-o-OH) (2-5), were synthesized by the reaction of 2-methylaminophenol with corresponding oxiranes. Titano-spiro-bis(ocanes) [MeN(CHR1CR2R3O)(C6H4-o-O)]2Ti 6-9 (2, 6, R1 = H, R2 = R3 = Me; 3, 7, R1 = R2 = Ph (treo-), R3 = H; 4, 8, R1 = Ph, R2 = R3 = H; 5, 9, R1 = R2 = H, R3 = Ph) based on [ONO]-ligands have been synthesized. The obtained compounds were characterized by 1H and 13C NMR spectroscopy and elemental analysis data. The complex [Ti(μ2-O){O-o-C6H4}{μ2-CMe2CH2}NMe]6 (10) was obtained by controlled hydrolysis of 6. Molecular structure of 10 was determined by X-ray structure analysis. 相似文献
10.
Christopher J. Davies 《Tetrahedron》2008,64(42):9857-9864
The anisyl boronic acids, 2-OMe-3-R2-5-R1-C6H2B(OH)2 (R1=R2=H (a); R1=H, R2=Ph (b); R1=Me, R2=H (c); R1=Cl, R2=H (d); R1=t-Bu, R2=H (e)), have been employed in Suzuki cross-coupling reactions with either 2-bromo-6-formylpyridine (I) or 2-bromo-6-acetylpyridine (II) generating, following a facile deprotection step, the 2-phenoxy-6-carbonylpyridines, 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-(CHO)C5H3N (R1=R2=H (1a); R1=Me, R2=H (1c); R1=Cl, R2=H (1d); R1=t-Bu, R2=H (1e)) and 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-(CMeO)C5H3N (R1=R2=H (2a); R1=H, R2=Ph (2b)). Condensation reactions of 1 and 2 with 2,6-diisopropylaniline proceed smoothly to give the 2-phenoxy-6-iminopyridines, 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-{CHN(2,6-i-Pr2C6H3)}C5H3N (R1=R2=H (3a); R1=Me, R2=H (3c); R1=Cl, R2=H (3d); R1=t-Bu, R2=H (3e)) and 2-(2′-OH-3′-R2-5′-R2-C6H2)-6-{CMeN(2,6-i-Pr2C6H3)}C5H3N (R1=H, R2=Ph (4a), R1=H, R2=Ph (4b)). Reduction of the imino unit (and concomitant C-C bond formation) in 3 can be achieved by treatment with trimethylaluminium or methyllithium which, following hydrolysis, furnishes the racemic chiral 2-phenoxy-6-(methanamino)pyridines, 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-{CHMe-NH(2,6-i-Pr2C6H3)}C5H3N (R1=R2=H (5a); R1=Me, R2=H (5c); R1=Cl, R2=H (5d); R1=t-Bu, R2=H (5e)). This work represents a straightforward and rapid synthetic route to libraries of sterically and electronically variable phenoxy-substituted imino- and methanamino-pyridines, which are expected to act as useful ligands or proligands for late and early transition metal-mediated alkene polymerisation catalysis. 相似文献
11.
Jérémie D.A. Pelletier 《Journal of organometallic chemistry》2006,691(19):4114-4123
The 2-imino-1,10-phenanthroline ligands, 1,10-C12H7N2-2-CRN(2,6-i-Pr2-4-R1-C6H2) [R = R1 = H (L1); R = H, R1 = Br (L2); R = H, R1 = CN (L3); R = H, R1 = i-Pr (L4); R = Me, R1 = H (L5); R = Me, R1 = i-Pr (L6)], have been prepared in high yield from the condensation reaction of 1,10-C12H7N2-2-CRO (R = H, Me) with one equivalent of the corresponding 4-substituted 2,6-diisopropylaniline. The molecular structures of L2, L5 and L6 reveal the imino nitrogen atoms to adopt a transoid configuration with respect to the phenanthrolinyl nitrogen atoms. Treatment of Lx with one equivalent of CoCl2 in n-BuOH at 90 °C gives the high spin complexes, (Lx)CoCl2 [Lx = L1 (1a), L2 (1b), L3 (1c), L4 (1d), L5 (1e), L6 (1f)], in which the metal centres exhibit distorted square pyramidal geometries. Activation of 1a-1f with excess methylaluminoxane (MAO) gives catalysts that are modestly active for the oligomerisation of ethylene affording mainly linear α-olefins along with some degree of internal olefins. While the donor capability of the 4-position of the N-aryl group does not appear to affect the activity of the catalyst, it does have an influence on the ratio of α-olefins to internal olefins. Single crystal X-ray diffraction studies have been performed on L2, L5, L6, 1a, 1c and 1f. 相似文献
12.
Denis A Kissounko 《Journal of organometallic chemistry》2003,683(1):29-38
Protonation of the trimethylenemethane derivatives, Cp*Zr(σ2,π-C4H6)[N(R1)C(Me)N(R2)] (1a: R1=R2=i-Pr and 1b: R1=Et, R2=t-Bu) (Cp*=η5-C5Me5), by [PhNMe2H][B(C6F5)4] in chlorobenzene at −10 °C provides the cationic methallyl complexes, Cp*Zr(η3-C4H7)[N(R1)C(Me)N(R2)] (2a: R1=R2=i-Pr and 2b: R1=Et, R2=t-Bu), which are thermally robust in solution at elevated temperatures as determined by 1H NMR spectroscopy. Addition of B(C6F5)3 to 1a and 1b provides the zwitterionic allyl complexes, Cp*Zr{η3-CH2C[CH2B(C6F5)3]CH2}[N(R1)C(Me)N(R2)] (3a: R1=R2=i-Pr and 3b: R1=Et, R2=t-Bu). The crystal structures of 2b and 3a have been determined. Neither the cationic complexes 2 or the zwitterionic complexes 3 are active initiators for the Ziegler-Natta polymerization of ethylene and α-olefins. 相似文献
13.
Six organotin compounds with 4,4′-thiodibenzenethiol (LH2) of the type RnSnL4−nSnRn (n = 3: R = Me 1, Ph 2, PhCH23, n = 2: R = Me 4, Ph 5, PhCH26) have been synthesized. All compounds were characterized by elemental analysis, IR and NMR (1H, 13C, and 119Sn) spectra. The structures of compounds 1, 2, 4, 5 and 6 were also determined by X-ray diffraction analysis, which revealed that compounds 1 and 2 were monomeric structures, compounds 4, 5 and 6 were centrosymmetric dinuclear macrocyclic structures, and all the tin(IV) atoms are four-coordinated. Furthermore, supramolecular structures were also found in compounds 1, 2, 4, 5 and 6, which exhibit one-dimensional chains, two-dimensional networks or three-dimensional structures through intermolecular C–H?S weak hydrogen bonds (WHBs), non-bonded Sn?S interactions or C–H?π interactions. 相似文献
14.
Six new chiral triorganotin(IV) complexes, {(R3Sn)2[C3H6(COO)2]}n (R = Me: 1; Bu: 2), {(R3Sn)2[C4H8(COO)2]}n (R = Me: 3; Bu: 4), and {(R3Sn)2[C2H4O(COO)2]}n (R = Me: 5; Bu: 6) have been prepared by treatment of (R)-(+)-methylsuccinic acid, (S)-(+)-methylglutaric acid and l-(−)-malic acid, with the corresponding R3SnCl (R = Me, Bu) and sodium ethoxide in methanol. All the complexes were characterized by elemental analysis, FT-IR, NMR (1H, 13C, 119Sn) spectroscopy and TGA. Except for 3, all of the complexes were also characterized by X-ray crystallography. The structural analyses reveal that complexes 1 and 5 have 2D network structures in which (R)-(+)-methylsuccinic acid and l-(−)-malic acid act as tetradentate ligands coordinated to trimethyltin(IV) ions. Complexes 2 and 4 have 3D metal-organic framework structures in which the deprotoned acids serve as tetradentate ligands. Complex 6 adopts a 1D zigzag chain structure and forms a 2D supramolecular framework through intermolecular C-H?O interactions. In addition, the antitumor activities of complexes 1-6 have been studied. We also have measured the specific rotation of the chiral dicarboxylic acids and the organotin derivatives. 相似文献
15.
A number of bridged half-sandwich titanium complexes [η5:η1-2-C5H4CHPh-4-R1-6-R2C6H2O]TiCl2 [R1 = H (5), Me (6), tBu (7, 8); R2 = H (6, 7), tBu (5, 8)] were synthesized from the reaction of their corresponding trimethylsilyl substituted ligand precursors 2-Me3SiC5H4CHPh-4-R1-6-R2C6H2OSiMe3 [R1 = H (1), Me (2), tBu (3, 4); R2 = H (2, 3), tBu (1, 4)] with TiCl4 in hexane. All new complexes were characterized by 1H and 13C NMR spectroscopy. Molecular structures of complexes 5 and 8 were determined by single crystal X-ray diffraction analysis. Upon activation with AliBu3/Ph3CB (C6F5)4, complexes 5-8 exhibit reasonable catalytic activity for ethylene polymerization and copolymerization with 1-hexene, producing polyethylene and poly(ethylene-co-1-hexene) with moderate molecular weights. 相似文献
16.
Ana E. Platero-Prats Concepción López Xavier Solans Piet W.N.M. van Leeuwen Gino P.F. van Strijdonck 《Journal of organometallic chemistry》2007,692(20):4215-4226
A study of the reactivity of enantiopure ferrocenylimine (SC)-[FcCHN-CH(Me)(Ph)] {Fc = (η5-C5H5)Fe{(η5-C5H4)-} (1a) with palladium(II)-allyl complexes [Pd(η3-1R1,3R2-C3H3)(μ-Cl)]2 {R1 = H and R2 = H (2), Ph (3) or R1 = R2 = Ph (4)} is reported. Treatment of 1a with 2 or 3 {in a molar ratio Pd(II):1a = 1} in CH2Cl2 at 298 K produced [Pd(η3-3R2-C3H4){FcCHN-CH(Me)(Ph)}Cl] {R2 = H (5a) or Ph (6a)}. When the reaction was carried out under identical experimental conditions using complex 4 as starting material no evidence for the formation of [Pd(η3-1,3-Ph2-C3H3){FcCHN-CH(Me)(Ph)}Cl] (7a) was found. Additional studies on the reactivity of (SC)-[FcCHN-CH(R3)(CH2OH)] {R3 = Me (1b) or CHMe2 (1c)} with complex 4 showed the importance of the bulk of the substituents on the palladium(II) allyl-complex (2-4) or on the ferrocenylimines (1) in this type of reaction. The crystal structure of 5a showed that: (a) the ferrocenylimine adopts an anti-(E) conformation and behaves as an N-donor ligand, (b) the chloride is in acis-arrangement to the nitrogen and (c) the allyl group binds to the palladium(II) in a η3-fashion. Solution NMR studies of 5a and 6a and [Pd(η3-1,3-Ph2-C3H3){FcCHN-CH(Me)(CH2OH)}Cl] (7b) revealed the coexistence of several isomers in solution. The stoichiometric reaction between 6a and sodium diethyl 2-methylmalonate reveals that the formation of the achiral linear trans-(E) isomer of Ph-CHCH-CH2Nu (8) was preferred over the branched derivative (9). A comparative study of the potential utility of ligand 1a, complex 5a and the amine (SC)-H2N-CH(Me)(Ph) (11) as catalysts in the allylic alkylation of (E)-3-phenyl-2-propenyl (cinnamyl) acetate with the nucleophile diethyl 2-methylmalonate (Nu−) is reported. 相似文献
17.
Investigation on coordination modes of organotin(IV) complexes with 6-thiopurine and related ligands
The organotin(IV) complexes R2Sn(tpu)2 · L [L = 2MeOH, R = Me (1); L = 0: R = n-Bu (2), Ph (3), PhCH2 (4)], R3Sn(Hthpu) [R = Me (5), n-Bu (6), Ph (7), PhCH2 (8)] and (R2SnCl)2 (dtpu) · L [L = H2O, R = Me (9); L = 0: R = n-Bu (10), Ph (11), PhCH2 (12)] have been synthesized, where tpu, Hthpu and dtpu are the anions of 6-thiopurine (Htpu), 2-thio-6-hydroxypurine (H2thpu) and 2,6-dithiopurine (H2dtpu), respectively. All the complexes 1-12 have been characterized by elemental, IR, 1H, 13C and 119Sn NMR spectra analyses. And complexes 1, 2, 7 and 9 have also been determined by X-ray crystallography, complexes 1 and 2 are both six-coordinated with R2Sn coordinated to the thiol/thione S and heterocyclic N atoms but the coordination modes differed. As for complex 7 and 9, the geometries of Sn atoms are distorted trigonal bipyramidal. Moreover, the packing of complexes 1, 2, 7 and 9 are stabilized by the hydrogen bonding and weak interactions. 相似文献
18.
A series of organotin (IV) complexes with 6-amino-1,3,5-triazine-2,4-dithiol of the type [(RnSnCl4−n)2 (C3H2N4S2)] (n = 3: R = Me 1, n-Bu 2, PhCH23, Ph 4; n = 2: R = Me 5, n-Bu 6, PhCH27, Ph 8) have been synthesized. All the complexes 1-8 have been characterized by elemental analysis, IR, 1H and 13C NMR spectra. Among them complexes 1, 4, 5 and 8 have also been characterized by X-ray crystallography diffraction analyses, which revealed that the tin atoms of complexes 1, 4, 5 and 8 are all five-coordinated with distorted trigonal bipyramid geometries. 相似文献
19.
A series of new triorganotin(IV) pyridinecarboxylates with 6-hydroxynicotinic acid (6-OH-3-nicH), 5-hydroxynicotinic acid (5-OH-3-nicH) and 2-hydroxyisonicotinic acid (2-OH-4-isonicH) of the types: [R3Sn (6-OH-3-nic)·L]n (I) (R = Ph, L = Ph·EtOH, 1; R = Bn, L = H2O·EtOH, 2; R = Me, L = 0, 3; R = n-Bu, L = 0, 4), [R3Sn (5-OH-3-nic)]n (II) (R = Ph, 5; R = Bn, 6; R = Me, 7; R = n-Bu, 8), [R3Sn (2-OH-4-isonic·L)]n (III) (R = Bn, 9, L = MeOH; R = Me, L = 0, 10; R = Ph, 11, L = 0.5EtOH) have been synthesized. All the complexes were characterized by elemental analysis, TGA, IR and NMR (1H, 13C, 119Sn) spectroscopy analyses. Among them, except for complexes 5 and 6, all complexes were also characterized by X-ray crystallography diffraction analysis. Crystal structures show that complexes 1-10 adopt 1D infinite chain structures which are generated by the bidentate O, O or N, O and the five-coordinated tin centers. Significant O-H?O, and N-H?O intermolecular hydrogen bonds stabilize these structures. Complex 11 is a 42-membered macrocycle containing six tin atoms, and forms a 2D network by intermolecular N-H?O hydrogen. 相似文献
20.
Mitsushiro Nomura Noriko SakamotoHirokazu Nakajima Chikako Fujita-TakayamaToru Sugiyama Masatsugu Kajitani 《Polyhedron》2011,30(17):2890-2895
Azido coordinated dithiolene complexes [CpCo(N3){S2C2(CO2Me)2}(S-CHR1R2)], where R1, R2 = H (4a); R1 = H, R2 = SiMe3 (4b); R1 = H, R2 = CO2Et (4c), were synthesized by the reactions of the corresponding Cl− coordinated precursors [CpCo(Cl){S2C2(CO2Me)2}(S-CHR1R2)] (3a-3c) with sodium azide. The Cl− coordinated complex 3d (R1, R2 = CO2Me) did not produce any N3− coordinated complexes but formed the CR1R2-bridged alkylidene adduct [CpCo{S2C2(CO2Me)2}(CR1R2)] (2d; R1, R2 = CO2Me). The structure of 4a was determined by X-ray diffraction study. In the molecular structure of 4a, the coordinated N3− ligand and CHR1R2 group were located at the same side with respect to the dithiolene ring (syn form), although the corresponding Cl− precursor (3a; R1, R2 = H) was anti form. A structural conversion of syn/anti was conceivable during the Cl−/N3− ligand exchange. Thermal (80 °C) and photochemical reactions (Hg lamp) of 4a-4c were performed. Among them, 4c was relatively well reacted compared with the others to form the CR1R2-bridged alkylidene adduct (2c; R1 = H, R2 = CO2Et), followed by a formal HN3 elimination, and the reaction also produced non-adduct of the cobalt dithiolene complex [CpCo{S2C2(CO2Me)2}] (1). The electrochemical 1e− reduction of 4c underwent a formal N3− ligand elimination, and successive second reduction caused the CHR1R2 group elimination or reformed the CR1R2-bridged alkylidene adduct 2c. 相似文献