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Reactions between HRuCl(PPh3)3 and 1,3- or 1,5-cyclooctadiene yield the 1,2-dihydropentalenyl complex (η5-C8H9)Ru(PPh3)2Cl through a series of steps including olefin insertion and electrocyclization. The reaction is accompanied by the loss of two equivalents of hydrogen. The product crystallizes in the monoclinic space group (No. 2). (η5-C8H9)Ru(PPh3)2Cl catalyzes the dimerization of phenylacetylene to a ≈2:1 mixture of Z:E 1,4-diphenyl-1-buten-3-yne. Comparison of the catalytic activity of (η5-C8H9)Ru(PPh3)2Cl with (η5-C5H5)Ru(PPh3)2Cl, (η5-C5Me5)Ru(PPh3)H3 and {η5-HB(pz)3}Ru(PPh3)2Cl suggests that the more electron-rich η5 ligands favor formation of the Z isomer. 相似文献
3.
Stefanus Otto Alfred Johannes Muller 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(12):1405-1407
The crystal structure of cis-[PtCl2(C6H15As)2], (I), is isostructural with a previously reported structure of cis-[PtCl2(C6H15P)2], (II). A new polymorph of (II) is also reported here. Selected geometrical parameters in the arsine complex are Pt—Cl 2.3412 (12) and 2.3498 (13), Pt—As 2.3563 (6) and 2.3630 (6) Å, Cl—Pt—Cl 88.74 (5), As—Pt—As 97.85 (2), and Cl—Pt—As 171.37 (4) and 177.45 (4)°. Corresponding parameters in the phosphine complex are Pt—Cl 2.364 (2) and 2.374 (2), Pt—P 2.264 (2) and 2.262 (2) Å, Cl—Pt—Cl 85.66 (9), P—Pt—P 98.39 (7), and Cl—Pt—P 170.26 (7) and 176.82 (8)°. 相似文献
4.
《Journal of organometallic chemistry》1992,426(2):C33-C35
The reaction at room temperature of [RuH(O2CCH3)(CO)(PPh3)2] (1) with β-nitrostyrene promotes the carbon-nitrogen bond cleavage a 相似文献
5.
Visweswara Rao Garimella Sridhar Yeleswarapu Hela Pamidipati Gayatri Padhi Trilochan Anipindi Nageswara Rao 《Transition Metal Chemistry》1999,24(5):566-570
The kinetics of substitution of Fe(tptz)2+2 by 2,2-bipyridine and 1,10-phenanthroline have been investigated in acetate buffers in the 3.6–5.6pH range employing stopped-flow spectrophotometry. These reactions are very fast and complete within 5s. The rate of substitution is linearly dependent on [phen] and [bpy]2, and increases with the increase in pH. Suitable mechanisms have been proposed involving the unprotonated form of the entering ligand, viz. bipyridine/phenanthroline as the reactive species. The pKa values of bipyridine and phenanthroline, determined from the kinetic data, are in agreement with the literature values. It is concluded that the substitutions of iron(II)-diimine complexes also occur by an associative mechanism. 相似文献
6.
Alkyne homocoupling is commonly observed in cross coupling reactions; however, self trimerization and homotetramerization of alkynes to form branched products through cross-coupling reactions are rarely reported. We describe herein homotrimerization and homotetramerization of terminal alkynes under the Sonogashira reaction conditions that gave the corresponding modified enediynes. Substrate scope for this reaction was explored. 相似文献
7.
Chiral nonracemic N-(diphenylphosphinoyl)-protected propargylic amines have been prepared by addition of terminal alkynes to N-(diphenylphosphinoyl)aldimines in the presence of dimethylzinc and 3,3′-dibromo-BINOL as catalyst. The reaction works with a variety of aromatic and heteroaromatic aldimines and with different alkynes, providing the expected products in generally good yields and enantiomeric excesses (up to 96%). 相似文献
8.
Stable bis(-diketonato) bridged binuclear complexes prepared by reacting [RuX3(EPh3)3] (X = Cl or Br; E = P or As) with (RCO)(MeCO)CH–Y–CH(COR)(COMe) [R = Me or Ph; Y = (CH2)6, (CH2)10] in a 2:1 molar ratio in benzene, have been characterised by elemental analyses, i.r., electronic, e.p.r. and cyclic voltammetry. The oxidation state of the metal ion in these complexes is confirmed as + 3 by electrochemical and by e.p.r. measurements. The complexes belong to a low-spin d5 configuration. An attempt has been made to ascertain the effect of the length of the bridging ligand on the electron transfer processes by cyclic voltammetry in these binuclear complexes. Based on the above studies an octahedral geometry has been tentatively proposed. The new complexes have been subjected to the antifungal activity studies. 相似文献
9.
The complex [(η6-p-cymene)Ru(μ-Cl)Cl]21 reacts with pyrazole ligands (3a-g) in acetonitrile to afford the amidine derivatives of the type [(η6-p-cymene)Ru(L)(3,5-HRR′pz)](BF4)2 (4a-f), where L = {HNC(Me)3,5-RR′pz}; R, R′ = H (4a); H, CH3 (4b); C6H5 (4c); CH3, C6H5 (4d) OCH3 (4e); and OC2H5 (4f), respectively. The ligand L is generated in situ through the condensation of 3,5-HRR′pz with acetonitrile under the influence of [(η6-p-cymene)RuCl2]2. The complex [(η6-C6Me6)Ru(μ-Cl)Cl]22 reacts with pyrazole ligands in acetonitrile to yield bis-pyrazole derivatives such as [(η6-C6Me6)Ru (3,5-HRR′pz)2Cl](BF4) (5a-b), where R, R′ = H (5a); H, CH3 (5b), as well as dimeric complexes of pyrazole substituted chloro bridged derivatives [{(η6-C6Me6)Ru(μ-Cl) (3,5-HRR′pz)}2](BF4)2 (5c-g), where R, R′ = CH3 (5c); C6H5 (5d); CH3, C6H5 (5e); OCH3 (5f); and OC2H5 (5g), respectively. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as analytical data. The molecular structures1 of representative complexes [(η6-C6Me6)Ru{3(5)-Hmpz}2Cl]+5b, [(η6-C6Me6)Ru(μ-Cl)(3,5-Hdmpz)]22+5c and [(η6-C6Me6)Ru(μ-Cl){3(5)Me,5(3)Ph-Hpz}]22+5e were established by single crystal X-ray diffraction studies. 相似文献
10.
《Journal of organometallic chemistry》1991,417(3):C59-C62
Reaction of [(η6-p-cymene)RuCl(L*)] with AgClO4 in Me2CO gives a perchlorate complex which on subsequent treatment with PPh3, γ-picoline or Cl− yields adducts showing that there can be retention as well as inversion of configuration at the metal centre. The (R)Ru,(SC absolute configurations of the chiral centres in the triphenylphosphine adduct have been established by an X-ray diffraction study [HL*, (S-α-methylbenzylsalicylaldimine]. The CD spectral study reveals that there is an inversion of configuration during formation of the PPh3 adduct. 相似文献
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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
13.
Rishikesh Prajapati Santosh Kumar Dubey Ruchi Gaur Raj Kumar Koiri Brajesh Kumar Maurya Surendra Kumar Trigun Lallan Mishra 《Polyhedron》2010
A synthetic precursor cis-[RuIICl2(dmso)4] is complexed separately with 3-(4-benzyloxyphenyl)-1-(2-hydroxylphenyl)-prop-2-en-1-one (L1H) and 2-(4-benzyloxyphenyl)-3hydroxy-chromen-4-one (L2H). The resulting complexes are assigned the composition fac-[RuCl(S-dmso)3(L1)] 1 and fac-[RuCl(S-dmso)3(L2)] 2 using elemental analyses, FAB mass data and spectroscopic (IR, 1H NMR, UV–Vis, emission) spectral properties. The X-ray diffraction analysis shows that complexes self-associate through non-covalent interactions and provide 1D and 2D supramolecular structures. These complexes are assayed for their cytotoxicity studies on Dalton Lymphoma cell lines. 相似文献
14.
Garimella Visweswara Rao Rajesh Bellam Nageswra Rao Anipindi 《Transition Metal Chemistry》2012,37(2):189-196
The substitution of bis(2,4,6-tripyridyl 1,3,5-triazine)iron(II),
\textFe(TPTZ) 2 2 + {\text{Fe(TPTZ)}}_{ 2}^{{ 2 { + }}} by 2,2′,6,2″-terpyridine (terpy) occurs on a time scale of about 6 m. The kinetics of this reaction was followed by stopped-flow
spectrophotometry in the pH range of 3.6–5.6 in acetate buffer. The data indicate that the reaction occurs in two consecutive
steps: kinetic data for both steps were acquired simultaneously and analyzed independently. The first step is assigned to
the reaction between
\textFe(TPTZ) 2 2 + {\text{Fe(TPTZ)}}_{ 2}^{{ 2 { + }}} and terpy to give Fe(TPTZ)(terpy)2+, followed by its reaction with another terpy molecule to give the final product,
\textFe(terpy) 2 2 + {\text{Fe(terpy)}}_{ 2}^{{ 2 { + }}} . The rate of the reaction increases with increases in [terpy] and pH. The kinetic and activation parameters determined for
both steps suggest that they involve both associative and dissociative paths. The ternary complex Fe(TPTZ)(terpy)2+ has been prepared, and the kinetics of its reaction with terpy suggest that this reaction is identical with the second step
of the
\textFe(TPTZ) 2 2 + {\text{Fe(TPTZ)}}_{ 2}^{{ 2 { + }}} -terpy system, supporting the proposed mechanism. 相似文献
15.
Transition Metal Chemistry - The rate and mechanism of substitution in the Ru(II) complexes (C1–C6) by thiourea nucleophiles was studied at pH 2 and rate constants measured as a function of... 相似文献
16.
A trinuclear bis(cyclohexanedioximate)(chloro)(nitrosyl)ruthenium(II) complex containing two (2,2-bipyridine)-copper(II) groups has been synthesized and its electronic and electrochemical properties investigated. According to ZINDO/S calculations, the electronic structure of the ruthenium(dioximate)(nitrosyl) moiety is strongly delocalized. The electrochemical behavior has been interpreted with the aid of spectroelectrochemical measurements. In the trinuclear complex, it has been shown that the copper(II) ions can promote the oxidation of the NO species generated electrochemically, and also mediate the redox reactions of the complex, under a dioxygen atmosphere. 相似文献
17.
《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1989,45(2):159-161
Pressure effects on the MLCT bands of the pyrazine- and 4-cyanopyridine-pentacyanoferrate(II) anions have been established. The relation of these piezochromic effects to the solvatochromism of each complex is put into the correlation between these parameters developed for other d6 ternary complexes. The conformance of piezochromic and solvatochromic efrects on MMCT bands for diiron and diruthenium mixed valence complexes to this correlation is examined. 相似文献
18.
《Tetrahedron letters》2014,55(50):6803-6807
Catalytic asymmetric Diels–Alder reactions of N-allenoyloxazolidinones were investigated. Various chiral metal–bis(oxazoline) and metal–pyridinebis(oxazoline) complexes were screened. Cu(SbF6)2(H2O)2(t-BuBox) was found to be the most effective catalyst, giving the product in high yield, enantioselectivity, and endo:exo selectivity. The relative reactivity between N-allenoyloxazolidinones and N-alkenoyloxazolidinones was also investigated. A model for stereoinduction was proposed to account for the enantioselectivity and endo:exo selectivity. 相似文献
19.
Phomphrai K Pongchan-o C Thumrongpatanaraks W Sangtrirutnugul P Kongsaeree P Pohmakotr M 《Dalton transactions (Cambridge, England : 2003)》2011,40(10):2157-2159
A series of bis(amidinate) tin(II) complexes is synthesized and shown to rapidly polymerize ε-caprolactone (ε-CL) in the presence and absence of benzyl alcohol giving high-molecular-weight poly(ε-CL) (M(n) up to 160,600 Da). Ligands having electron donating groups were found to accelerate the polymerization by making the complex more nucleophilic. 相似文献
20.
Gregorio Sánchez Joaquín García Juan J. Ayllón José L. Serrano Luis García José Pérez Gregorio López 《Polyhedron》2007
The dimeric starting material [Ru(η6-p-cymene)(μ-Cl)Cl]2 reacts with the phosphino-amides o-Ph2P–C6H4CO–NH–R [R = iPr (a), Ph (b), 4-MeC6H4 (c), 4-FC6H4 (d)] to give the mononuclear compounds 1a–d [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–NH–R)]Cl. The subsequent reaction of these complexes with KPF6 produced the cationic species 2a–d [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–NH–R)][PF6] in which phosphino-amides also act as rigid P,O-chelating ligands. The molecular structures of 2b–d were determined crystallographically. Amide deprotonation is achieved when complexes 2a–d were made react with 1 M aqueous solution of KOH, affording the corresponding neutral species 3a–d [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–N–R)] in which a P,N-coordination mode is suggested. 相似文献