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1.
Cornelia Borgmann Christian Limberg Elisabeth Kaifer Hans Pritzkow Lszl Zsolnai 《Journal of organometallic chemistry》1999,580(2):10099
The reaction of Mo(η3-C3H4(CH3))(CH3CN)2(CO)2Cl with AgBF4 in THF yields the cationic complex [Mo(η3-C3H4(CH3))(CH3CN)2(CO)2(THF)]+[BF4]−, 1, whose X-ray structure has been determined. Oxo nucleophiles are capable of replacing the weakly bound THF molecule in 1 and under simultaneous loss of CH3CN the resulting complexes aggregate to oligonuclear compounds. Accordingly, the reactions with NaOMe and KOH yield [Na(THF)4]+[(η3-C3H4(CH3))(CO)2Mo(μ-OCH3)3Mo(CO)2(η3-C3H4(CH3))]−, 2 and [K(18-crown-6)]+[[Mo(η3-C3H4(CH3))(CO)2]3(μ2-OH)3(μ3-OH)]−, 3, which were characterized by means of single crystal X-ray diffraction. Due to fluoride abstraction from BF4− the reaction of 1 with KOH also yields fluorinated derivatives of 3 but incorporation of fluorine in 3 can be avoided if AgO3SCF3 rather than AgBF4 is used to generate the cation of 1. For purposes of comparison the dinuclear complex [K(18-crown-6)]+[[Mo(η3-C3H4(CH3))(CO)2]2(μ2-F)3]−, 4, has been prepared, too, showing fluoride bridges and KF bonding. The chemical properties and the structures of these compounds in solution as well as their role as structural models for intermediates during molybdenum oxide catalysed propene oxidation are discussed. 相似文献
2.
Reaction of [Cp* RuCl2]2 with
-alanine (
-alaH) in methanol at room temperature in the presence of NaOMe yields the complex Na[Cp* RuCl(
-ala)] (1), which contains a five-membered N,O-coordinated chelate ring. The analogous complex Na[Cp* RuCl(
-phe)] (2) is obtained under similar conditions but at 0°C in 90% yield. At temperatures above 20°C both 2 and the η6-coordinated complex [Cp* Ru(
-pheH)]Cl (4) are obtained, with the proportion of the latter increasing with temperature. Compound 4 is obtained in 88% yield by refluxing [Cp* RuCl2]2 and
-phenylalanine (
-pheH) in CH3OH/CH3ONa followed by separation from 2. The analogous ruthenium(II) sandwich complexes 5–10 were obtained from
-tyrosine and
-tryptophane and various derivatives. [Cp* Ru(
-met)] (3), prepared by the reaction of [Cp* RuCl2]2 with
-methionine (
-metH) in CH3OH/CH3ONa, displays N,O,S-coordination. 相似文献
3.
The Reactions of M[BF4] (M = Li, K) and (C2H5)2O·BF3 with (CH3)3SiCN. Formation of M[BFx(CN)4—x] (M = Li, K; x = 1, 2) and (CH3)3SiNCBFx(CN)3—x, (x = 0, 1) The reaction of M[BF4] (M = Li, K) with (CH3)3SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BFx(CN)4—x] (x = 1, 2; M = Li, K). By using (C2H5)2O·BF3 the synthesis yields the compounds (CH3)3SiNCBFx(CN)3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF2(CN)2]·2Me3SiCN Cmc21, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) Å3, Z = 12, R1 = 4.7%; K[BF2(CN)2] P41212, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) Å3, Z = 48, R1 = 2.5%; K[BF(CN)3] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) Å3, Z = 2, R1 = 3.6%; Me3SiNCBF(CN)2 Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) Å3, Z = 8, R1 = 4.4% 相似文献
4.
Stanisaw Krompiec Robert Penczek Mateusz Penkala Micha Krompiec Jzef Rzepa Marek Matlengiewicz Joanna Jaworska Stefan Baj 《Journal of molecular catalysis. A, Chemical》2008,290(1-2):15-22
Addition of alcohols and phenols to allyl ethers catalyzed mainly by ruthenium complexes was studied. Complexes of ruthenium generated in situ from precursors such as {[RuCl2(1,5-COD)]x} or [Ru3(CO)12] and from external ligands such as phosphines (e.g. PPh3, PBu3, BINAP) or phosphites (e.g. P(OPh)3, P(OMe)3) were found to be particularly efficient catalysts of the studied reactions. Transacetalization reaction could be practically completely eliminated by the addition of a base (particularly Na2CO3) to the catalytic systems. It was observed that the selectivity of mixed acetals formation increases with increasing value of Θ parameter of phosphines. Especially interesting results (0–5% of transacetalization) have been obtained for catalytic systems generated from {[RuCl2(1,5-COD)]x} or [Ru3(CO)12], phosphines (PPh3, BINAP, dppe, tris(2,4,6-tri-metylphenyl)phosphine, or dppf) and Na2CO3. The mechanism of mixed acetals formation has been investigated using deuterated reagents. It is postulated that the examined reaction is a nucleophilic addition of ROH to a hydrido-π-allyl complex formed during oxidative addition of allyl substrate to metal complex. As a result, a new, selective, and convenient method of the synthesis of symmetrical and, in particular, unsymmetrical (mixed) acetals has been developed. Mixed acetals CH3CH2CH(OR1)(OR2) may be obtained in the reaction of R1-O-allyl with R2OH or R1OH with R2-O-allyl, depending on the structure of R1 and R2. 相似文献
5.
Cyanide Bridged Coordination Polymers from cis‐ or trans‐[Ru(tBuNC)4(CN)2] and MnCl2: About the Influence of Different Topologies on the Magnetic Properties of Materials The reaction of cis‐ or trans‐[Ru(tBuNC)4(CN)2] with MnCl2 as an additional transition metal fragment yields the one dimensional coordination polymers {cis‐[Ru(CN)2(tBuNC)4] MnCl2}n, ( 1 ), and {trans‐[Ru(CN)2(tBuNC)4]MnCl2}n, ( 2 ), with a different arrangement of the metal centers caused by the different stereochemistry of the starting compounds. The variation of the Ru‐C‐N‐Mn geometry nevertheless leads to significant differences in the magnetic properties of 1 and 2 . The coordination polymer derived from trans‐[Ru(tBuNC)4(CN)2] shows a more efficient antiferromagnetic intrachain interaction between the manganese centers compared to the cis‐derivative. 相似文献
6.
Marie-Noëlle Collomb-Dunand-Sauthier Alain Deronzier Raymond Ziessel 《Journal of Electroanalytical Chemistry》1993,350(1-2)
The clectrochemical behaviour of the complexes [RuII(L)(CO)2Cl2], [RuII(L)(CO)Cl3][Me4N] and [RuII(L)(CO)2(CH3CN)2][CF3SO3]2 (L = 2,2′-bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine) has been investigated in CH3CN. The oxidation of [Ru(L)(CO)2Cl2] produces new complexes [RuIII(L)(CO)(CH3CN)2Cl]2+ as a consequence of the instability of the electrogenerated transient RuIII species [RuIII(L)(CO)2Cl2]+. In contrast, the oxidation of [RuII(L)(CO)Cl3][Me4N] produces the stable [RuIII(L)(CO)Cl3] complex. In contrast [RuII(L)(CO)2(CH3CN)2][CF3SO3]2 is not oxidized in the range up to the most positive potentials achievable. The reduction of [RuII(L)(CO)2Cl2] and [RuII(L)(CO)2(CH3CN)2][CF3SO3]2 results in the formation of identical dark blue strongly adherent electroactive films. These films exhibit the characteristics of a metal-metal bond dimer structure. No films are obtained on reduction of [RuII(L)(CO)Cl3][Me4N]. The effect of the substitution of the bipyridine ligand by electron-withdrawing carboxy ester groups on the electrochemical behaviour of all these complexes has also been investigated. 相似文献
7.
Solvolysis of [RhMe(CF3SO3)2(Me3[9]aneN3)] ( 1 ) (Me3[9]aneN3 = 1, 4, 7‐trimethyl‐1, 4, 7‐triazacyclononane) in CH3CN, DMSO or pyrazole (L) leads to substitution of both trifluoromethylsulfonate ligands and formation of the cationic complexes [RhMeL2(Me3[9]aneN3)](CF3SO3)2 3—5 . In contrast, treatment of [RuCl3(Me3[9]aneN3)] ( 2 ) with Ag(CF3SO3) in a 1:3 ratio for 2h in CH3CN leads to formation of the tetranuclear complex [{RuCl3(Me3[9]aneN3)}2Ag2(CF3SO3)(CH3CN)](CF3SO3) · CH3CN ( 6 ) with a novel [(RuCl3)2Ag2] core. More forcing conditions enable the substitution of respectively one or two chloride ligands by CH3CN (reflux 18h) or DMF (85°C, 1h) to afford [RuCl2(CH3CN)(Me3[9]aneN3)](CF3SO3) ( 7 ) and [RuCl(DMF)2(Me3[9]aneN3)](CF3SO3)2 ( 8 ). The heteroleptic sandwich complex [Ru([9]aneS3)(Me3[9]aneN3)](CF3SO3)2 ( 9 ) can be prepared by reduction of 2 with Zn powder in acetone in the presence of 3 equiv. of Ag(CF3SO3), followed by addition of [9]aneS3 (1, 4, 7‐trithiacyclononane). The redox potential E°(Ru3+/Ru2+) of +1.87 V vs NHE for 9 is only —0.12 V lower than that of the homoleptic complex [Ru([9]aneS3)2]2+. Crystal structures are reported for 3 — 9 . 相似文献
8.
Georg Wolfbauer Alan M. Bond Glen B. Deacon Douglas R. MacFarlane Leone Spiccia 《Journal of Electroanalytical Chemistry》2000,490(1-2)
The electrochemical reduction of the black dye photosensitizer [(H3-tctpy)RuII(NCS)3]− (H3-tctpy=2,2′:6′,2′′-terpyridine-4,4′,4′′-tricarboxylic acid) used in photovoltaic cells has been found to be a complex process when studied in dimethylformamide. At low temperatures, fast scan rates and at a glassy carbon electrode, the chemically reversible ligand based one-electron reduction process [(H3-tctpy)Ru(NCS)3]−+e−[(H3-tctpy√−)Ru(NCS)3]2− is detected. This process has a reversible half-wave potential (Er1/2) of −1585±20 mV versus Fc/Fc+ at 25°C. Under other conditions, a deprotonation reaction occurs upon reduction, which produces [(H3−x-tctpyx−)Ru(NCS)3](1+x)− and hydrogen gas. Mechanistic pathways giving rise to the final products are discussed. The Er1/2-value for the ligand based reductions of the deprotonated complex is 0.70 V more negative than for [(H3-tctpy)Ru(NCS)3]−. Consequently, data obtained from molecular orbital calculations are consistent with the reaction [(H3-tctpy)Ru(NCS)3]−+e−→[(H2-tctpy−)Ru(NCS)3]2−+1/2H2 yielding the monodeprotonated complex as the major product obtained after electrochemical reduction of [(H3-tctpy)Ru(NCS)3]−. The Er1/2-values for the metal based RuII/III process differ by 0.30 V when data obtained for the protonated and deprotonated forms of the black dye are compared. Electronic spectra obtained during the course of experiments in an optically transparent thin layer electrolysis configuration are consistent with the overall reaction scheme proposed on the basis of voltammetric measurements and molecular orbital calculations. Reduction studies on the free ligand, H3-tcpy, are consistent with results obtained with [(H3-tctpy)Ru(NCS)3]−. 相似文献
9.
Synthesis and Dynamic Behaviour of [Rh2(μ-H)3H2(PiPr3)4]+. Contributions to the Reactivity of the Tetrahydridodirhodium Complex [Rh2H4(PiPr3)4] An improved synthesis of [Rh2H4(PiPr3)4] ( 2 ) from [Rh(η3-C3H5)(PiPr3)2] ( 1 ) or [Rh(η3-CH2C6H5)(PiPr3)2] ( 3 ) and H2 is described. Compound 2 reacts with CO or CH3OH to give trans-[RhH(CO)(PiPr3)2] ( 4 ) and with ethene/acetone to yield a mixture of 4 and trans-[RhCH3(CO)(PiPr3)2] ( 5 ). The carbonyl(methyl) complex 5 has also been prepared from trans-[RhCl(CO)(PiPr3)2] ( 6 ) and CH3MgI. Whereas the reaction of 2 with two parts of CF3CO2H leads to [RhH2(η2-O2CCF3) · (PiPr3)2] ( 8 ), treatment of 2 with one equivalent of CF3CO2H in presence of NH4PF6 gives the dinuclear compound [Rh2H5(PiPr3)4]PF6 ( 9a ). The reactions of 2 with HBF4 and [NO]BF4 afford the complexes [Rh2H5(PiPr3)4]BF4 ( 9b ) and trans-[RhF(NO)(PiPr3)2]BF4 ( 11 ), respectively. In solution, the cation [Rh2(μ-H)3H2(PiPr3)4]+ of the compounds 9a and 9b undergoes an intramolecular rearrangement in which the bridging hydrido and the phosphane ligands are involved. 相似文献
10.
Sebastian Scharf Eduard Kovalski Tobias Rüffer Alexander Hildebrandt Heinrich Lang 《无机化学与普通化学杂志》2020,646(22):1820-1833
The synthesis of [Ti6O4(OiPr)8(O2CPh)8] ( 3 ) and [RuCl(N≡CR)5][RuCl4(N≡CR)2] ( 4a , R = Me; 4b , R = Ph), [Ru(N≡CPh)6][RuCl4(N≡CPh)2] ( 5 ) and [H3O][RuCl4(N≡CMe)2] ( 7a ) is discussed. Crystallization of 5 from CH2Cl2 gave trans-[RuCl2(N≡CPh)4] ( 6 ). The solid-state structures of 3 , 4a , b , 5 , 6 and 7a are reported. Complex 4b forms a 3D network, while 6 displays a 2D structure, due to π-interactions between the benzonitrile ligands. The (spectro)electrochemical behavior of 4a , b and 6 was studied at 25 and –72 °C and the results thereof are compared with [NEt4][RuCl4(N≡CMe)2] ( 7b ) and [RuCl(N≡CPh)5][PF6] ( 8 ). The electrochemical response of the cation and the anion in 4a , b are independent from each other. [RuCl(N≡CR)5]+ possesses one reversible RuII/RuIII process. However, [RuCl4(N≡CMe)2]– was shown to be prone to ligand exchange and disproportionation upon formation of either a RuIV and RuII species at 25 °C, while at –72 °C the rapid conversion of the electrochemically formed species is hindered. In situ IR and UV/Vis/NIR studies confirmed the respective disproportionation reaction products of the aforementioned oxidation and reduction, respectively. 相似文献
11.
Garth Cripps Sylvie Chardon-Noblat Alain Deronzier 《Journal of organometallic chemistry》2004,689(2):484-488
The selective in situ synthesis of trans and cis(CH3CN)-[Ru(bpy)(CO)2 (CH3CN)2]2+ isomers from the same [Ru(CO)2 (CH3CN)3]22+ dimer precursor but using either an electrochemical-chemical or chemical-electrochemical process is described. 相似文献
12.
S5N5⊕[RuCl3(CO)3]⊖ · 0.5 CH2Cl2. Synthesis, I.R. Spectrum and Crystal Structure S5N5[RuCl3(CO)3] · 0.5 CH2Cl2 is prepared from Ru3(CO)12 and trithiazylchloride in boiling dichloromethane; it forms red crystals, which are characterized by it's IR spectrum and by structural determination with X-ray methods. The compound crystallizes monoclinic in the space group C2/c with 8 formula units per unit cell. The lattice dimensions are a = 2047, b = 1064, c = 1637 pm, β = 96.1° (3487 independent, observed reflexions, R = 0.075). The structure consists of planar, cyclic S5N5⊕ cations in the “azulene” conformation with bond lengths SN from 155 to 159 pm, and octahedral [RuCl3(CO)3]⊖ anions with fac-geometry and bond lengths Ru Cl of 242 pm and Ru C of 185 to 190 pm. 相似文献
13.
T.K. Mondal J.-S. Wu T.-H. Lu Sk. Jasimuddin C. Sinha 《Journal of organometallic chemistry》2009,694(21):3518-3525
The reaction of 1-alkyl-2-{(o-thioalkyl)phenylazo}imidazoles (SRaaiNR) (2a/2b) with Ru(II) has synthesized [Ru(SRaaiNR)2](ClO4)2 (3a/3b) in 2-methoxyethanol. The reaction in methanol, however, has synthesized [Ru(SRaaiNR)(SRaaiNR)Cl](ClO4) (4a/4b). The solid phase reaction of SRaaiNR and RuCl3 on silica gel surface upon microwave irradiation has synthesized [Ru(SRaaiNR)(SaaiNR)](PF6) (5a/5b) [SRaaiNR represents tridentate N,N′,S-chelator; SRaaiNR is N,N′-bidentate chelator where S does not coordinate and SaaiNR refers N,N′,S-chelator where S refers to thiolato binding]. The structural characterization of [Ru(SEtaaiNEt)(SEtaaiNEt)Cl](ClO4) (4b) and [Ru(SEtaaiNEt)(SaaiNEt)](PF6) (5b) has been confirmed by single crystal X-ray diffraction study. The IR, UV–Vis, and 1H NMR spectral data also support the stereochemistry of the complexes. The complexes show metal oxidation, Ru(III)/Ru(II), and ligand reductions (azo/azo−, azo−/azo). The molecular orbital diagram has been drawn by density functional theory (DFT) calculation. Normal mode of analysis has been performed to correlate calculated and experimental frequencies of representative complexes. The electronic movement and assignment of electronic spectra have been carried out by TDDFT calculation both in gas and acetonitrile phase. 相似文献
14.
Moumita Majumdar Arup Sinha Tapas Ghatak Sanjib K. Patra Nabanita Sadhukhan S. M. Wahidur Rahaman Jitendra K. Bera Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(8):2574-2585
The complete sequence of reactions in the base‐promoted reduction of [{RuII(CO)3Cl2}2] to [RuI2(CO)4]2+ has been unraveled. Several μ‐OH, μ:κ2‐CO2H‐bridged diruthenium(II) complexes have been synthesized; they are the direct results of the nucleophilic activation of metal‐coordinated carbonyls by hydroxides. The isolated compounds are [Ru2(CO)4(μ:κ2‐C,O‐CO2H)2(μ‐OH)(NPF‐Am)2][PF6] ( 1 ; NPF‐Am=2‐amino‐5,7‐trifluoromethyl‐1,8‐naphthyridine) and [Ru2(CO)4(μ:κ2‐C,O‐CO2H)(μ‐OH)(NP‐Me2)2][BF4]2 ( 2 ), secured by the applications of naphthyridine derivatives. In the absence of any capping ligand, a tetranuclear complex [Ru4(CO)8(H2O)2(μ3‐OH)2(μ:κ2‐C,O‐CO2H)4][CF3SO3]2 ( 3 ) is isolated. The bridging hydroxido ligand in 1 is readily replaced by a π‐donor chlorido ligand, which results in [Ru2(CO)4(μ:κ2‐C,O‐CO2H)2(μ‐Cl)(NP‐PhOMe)2][BF4] ( 4 ). The production of [Ru2(CO)4]2+ has been attributed to the thermally induced decarboxylation of a bis(hydroxycarbonyl)–diruthenium(II) complex to a dihydrido–diruthenium(II) species, followed by dinuclear reductive elimination of molecular hydrogen with the concomitant formation of the RuI? RuI single bond. This work was originally instituted to find a reliable synthetic protocol for the [Ru2(CO)4(CH3CN)6]2+ precursor. It is herein prescribed that at least four equivalents of base, complete removal of chlorido ligands by TlI salts, and heating at reflux in acetonitrile for a period of four hours are the conditions for the optimal conversion. Premature quenching of the reaction resulted in the isolation of a trinuclear RuI2RuII complex [{Ru(NP‐Am)2(CO)}{Ru2(NP‐Am)2(CO)2(μ‐CO)2}(μ3:κ3‐C,O,O′‐CO2)][BF4]2 ( 6 ). These unprecedented diruthenium compounds are the dinuclear congeners of the water–gas shift (WGS) intermediates. The possibility of a dinuclear pathway eliminates the inherent contradiction of pH demands in the WGS catalytic cycle in an alkaline medium. A cooperative binuclear elimination could be a viable route for hydrogen production in WGS chemistry. 相似文献
15.
Helena Brake Eugenia Peresypkina Alexander V. Virovets Martin Piesch Werner Kremer Lisa Zimmermann Christian Klimas Manfred Scheer 《Angewandte Chemie (International ed. in English)》2020,59(37):16241-16246
In a high‐yield one‐pot synthesis, the reactions of [Cp*M(η5‐P5)] (M=Fe ( 1 ), Ru ( 2 )) with I2 resulted in the selective formation of [Cp*MP6I6]+ salts ( 3 , 4 ). The products comprise unprecedented all‐cis tripodal triphosphino‐cyclotriphosphine ligands. The iodination of [Cp*Fe(η5‐As5)] ( 6 ) gave, in addition to [Fe(CH3CN)6]2+ salts of the rare [As6I8]2? (in 7 ) and [As4I14]2? (in 8 ) anions, the first di‐cationic Fe‐As triple decker complex [(Cp*Fe)2(μ,η5:5‐As5)][As6I8] ( 9 ). In contrast, the iodination of [Cp*Ru(η5‐As5)] ( 10 ) did not result in the full cleavage of the M?As bonds. Instead, a number of dinuclear complexes were obtained: [(Cp*Ru)2(μ,η5:5‐As5)][As6I8]0.5 ( 11 ) represents the first Ru‐As5 triple decker complex, thus completing the series of monocationic complexes [(CpRM)2(μ,η5:5‐E5)]+ (M=Fe, Ru; E=P, As). [(Cp*Ru)2As8I6] ( 12 ) crystallizes as a racemic mixture of both enantiomers, while [(Cp*Ru)2As4I4] ( 13 ) crystallizes as a symmetric and an asymmetric isomer and features a unique tetramer of {AsI} arsinidene units as a middle deck. 相似文献
16.
Priti SinhaDushyant Singh Raghuvanshi Krishna Nand SinghLallan Mishra 《Polyhedron》2012,31(1):227-234
The known compound 4′-(carboxyphenyl)-2,2′:6,2″-terpyridine (LH) was prepared and complexed with RuCl3.3H2O. The resulting complex [Ru(LH)Cl3] was then allowed to react separately with 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), triphenylphosphine (PPh3) and 1,2-bis-(diphenylphosphino)ethane (dppe). The compositions of corresponding complexes [Ru(LH)bpyCl](BF4) 1, [Ru(LH)phenCl](BF4) 2, [Ru(LH)(PPh3)(CH3CN)2] (BF4)23 and [Ru(LH)(dppe)Cl](BF4) 4 were assigned on the basis of their FAB-mass spectra, elemental analysis, spectroscopic (IR, NMR) data and X-ray diffraction measurements. The diamagnetic, cationic complexes displayed strong MLCT transitions in the visible region with significant shift in MLCT band energy corresponding to the strength of substituted ligands. The redox behaviour of the complexes was investigated using cyclic voltammetry measurements. Among all the complexes, 3 efficiently catalyzed the synthesis of propargylamine via three components coupling reaction. 相似文献
17.
Neutral and Cationic Ruthenium(II) Complexes with Trifunctional Phosphane Ligands Compounds of the type [RuCl2(RPX2)2] 4 – 7 (R = iPr, tBu; X = CH2CH2OMe, CH2CO2Me) were prepared by reacting RPX2 with either RuCl3 · 3H2O or [RuCl2(PPh3)3], respectively. In 4 – 7 the trifunctional phosphanes coordinate as bidentate ligands to the metal center through the phosphorus atom and the oxygen atom of a methoxy or carbonyl group. The lability of the Ru–O bond allows substitution reactions with CO, tert-butylisonitrile and phenylacetylene. The Ru–Cl bonds in 5 (R = tBu; X = CH2CH2OMe) can be cleaved upon treatment with one or two equiv of AgPF6 yielding mono- or dicationic derivatives. In these complexes the ligands are coordinated to the metal center through the phosphorus and both of the oxygen donor atoms. The reaction of the phosphinoesterenolate compound 17 with Ph2C=C=O leads to the insertion of two molecules of the ketene into the C–H bond of one of the five-membered metal-enolate rings to yield the “expanded” chelate complex 18 , the structure of which was determined by X-ray crystallography. 相似文献
18.
Reactivity of [M2(μ‐Cl)2(cod)2] (M=Ir,Rh) and [Ru(Cl)2(cod)(CH3CN)2] with Na[H2B(bt)2]: Formation of Agostic versus Borate Complexes
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K. Bakthavachalam K. Yuvaraj Mohammad Zafar Prof. Dr. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17291-17297
Treatment of [M2(μ‐Cl)2(cod)2] (M=Ir and Rh) with Na[H2B(bt)2] (cod=1,5‐cyclooctadiene and bt=2‐mercaptobenzothiazolyl) at low temperature led to the formation of dimetallaheterocycles [(Mcod)2(bt)2], 1 and 2 ( 1 : M=Ir and 2 : M=Rh) and a borate complex [Rh(cod){κ2‐S,S′‐H2B(bt)2}], 3 . Compounds 1 and 2 are structurally characterized metal analogues of 1,5‐cyclooctadiene. Metal–metal bond distances of 3.6195(9) Å in 1 and 3.6749(9) Å in 2 are too long to consider as bonding. In an attempt to generate the Ru analogue of 1 and 2 , that is [(Rucod)2(bt)2], we have carried out the reaction of [Ru(Cl)2(cod)(CH3CN)2] with Na[H2B(bt)2]. Interestingly, the reaction yielded agostic complexes [Ru(cod)L{κ3‐H,S,S′‐H2B(bt)2}], 4 and 5 ( 4 : L=Cl; 5 : L=C7H4NS2). One of the key differences between 4 and 5 is the presence of different ancillary ligands at the metal center. The natural bond orbital (NBO) analysis of 1 and 2 shows that there is four lone pairs of electrons on each metal center with a significant amount of d character. Furthermore, the electronic structures and the bonding of these complexes have been established on the ground of quantum‐chemical calculations. All of the new compounds were characterized by IR, 1H, 11B, 13C NMR spectroscopy, and X‐ray crystallographic analysis. 相似文献
19.
The crystal structure of K[BF3(CN)] (Pbcn (Nr. 60) with a = 13.3486(15) b = 6.5239(7) c = 10.0085(11) Å, and eight formula units per unit cell) has been determined and the one of K[BF2(CN)2] was confirmed and improved. The different networks in the complete series of borates K[BFx(CN)4–x], x = 0–4 are compared and discussed. 相似文献
20.
The cis-[Mn(CO)4(TePh)2]?, similar to bidentate ligand PhTe(CH2)3TePh, acts as a “chelating metalloligand” for the synthesis of metallic tellurolate compounds. The reaction of cis[Mn(CO)4(TePh)2]? with BrMn(CO)5 in THF leads to a mixture of products[(CO)3,BrMn(μ-TePh)2Mn(CO)4]? (1) and Mn2(μ-TePh)2(CO)g (2). Complex 1 crystallizes in the triclinic space group Pl? with a = 11.309(3) Å, b = 14.780(5) Å, c = 19.212(6) Å, a = 76.05(3)° β = 72.31(3)°, γ = 70.41(3)° V = 2848(2) Å3, Z = 2. Final R = 0.034 and Rw = 0.035 resulting from refinement of 10021 total reflections with 677 parameters, Dropwise addition of (MeTe)2 to a solution of [Me3O][BF4] in CH3CN leads to formation of [Me2TeTeMe][BF4], a potential MeTe+ donor ligand. In contrast to oxidative addition of diphenyl ditelluride to [Mn(CO)s]? to give cis-[Mn(CO)4(TePh)2]? which was thermally transformed into [(CO)3Mn(μ-TePh)3Mn(CO)3]?, reaction of [Mn(CO)5]?with [Me2TeTeMe]+ proceeded to give the monomeric species MeTeMn(CO)5 as initial product which was then dimerized into Mn2(μ-TeMe)2(CO)g (4). 相似文献