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1.
The reaction of exo-nido-ruthenacarborane exo-nido-5,6,10-[Cl(Ph 3P) 2Ru]-5,6,10-(-H) 3-10-H-7,8-C 2B 9H 8 ( 1) with the 8-trifluoroacetoxymercury derivative of ferracarborane 3-( 5-Cp)-4-SMe 2-8-CF 3COOHg-3,1,2-FeC 2B 9H 9 ( 2) was studied. It was demonstrated for the first time that metallacarborane 2 can be used as a mercurating agent. The reaction afforded 5",6",10" -exo-nido-[Cl(Ph 3P) 2Ru]-5",6",10"-(-H) 3-10"-{3-( 5-Cp)-4-SMe 2-3,1,2-FeC 2B 9H 9-8-Hg}-7",8"-C 2B 9H 8 ( 3) existing as two isomers. The structure of trans isomer 3a was established by X-ray diffraction analysis. 相似文献
2.
The reaction of bromine with exo-nido-ruthenacarborane [Cl(Ph 3P) 2Ru]-5,6,10-(-H) 3-10-H-7,8-C 2B 9H 8 ( 1) led to the replacement of the chlorine atom by the bromine atom in the octahedral environment of the ruthenium atom rather than to the substitution in the carborane cage. The structure of [Br(Ph 3P) 2Ru]-5,6,10-(-H) 3-10-H-7,8-C 2B 9H 8 was established by NMR and IR spectroscopy and X-ray diffraction analysis. 相似文献
3.
The structures of the metallacarborane cations [(-9-Me 2S-7,8-C 2B 9H 10)Ni(-Cp)Ni(-9-Me 2S-7,8-C 2B 9H 10)] + ( 2) and [Cp*Ru(Me 2S-C 2B 9H 10)RuCp*] + ( 4b) were established by X-ray diffraction analysis. These results confirmed the triple-decker structure proposed for complex 2 earlier, whereas complex 4b proved to be 13-vertex dimetallacarborane rather than the triple-decker complex, as has been suggested earlier.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1883, September, 2004. 相似文献
4.
The reaction of OsCl 2(PPh 3) 3 with [ nido-7-R 1-8-R 2-C 2B 9H 10]K + produced a series of new exo-nido-osmacarborane complexes exo-nido-5,6,10-[Cl(Ph 3P) 2Os]-5,6,10-(-H) 3-10-H-7-R 1-8-R 2-7,8-C 2B 9H 6 ( 1: R 1 = R 2 = H; 2: R 1 = R 2 = Me; 3: R 1 = R 2 = PhCH 2; 4: R 1 + R 2 = 1,2-C 6H 4(CH 2) 2; 5: R 1 = H, R 2 = Me) in which the osmium-containing group is linked to the nido-carborane ligand through three two-electron three-center bonds. Compounds 1— 5 are formed as mixtures of symmetric ( a) and asymmetric ( b) isomers; pure symmetric isomers 2a and 4a were isolated by fractional crystallization, and the mixture of isomers 3a, was quantitatively separated into individual compounds 3a and 3b by column chromatography on silica gel. Detailed analysis of the 31P{ 1H}, 1H, 11B NMR spectra of 1a,b— 5a,b and 2D 1H- 1H{ 11B} and 11B{ 1H}- 11B{ 1H} NMR spectra of 3a and 3b was performed. The structures of isomers 2a and 4a were confirmed by an X-ray diffraction study. According to the NMR and X-ray diffraction data, the isomerism of exo-nido-complexes 1a,b— 5a,b is actually the cis— trans-isomerism of ligand arrangement in the octahedral coordination of the Os atom. 相似文献
5.
A series of diastereomeric closo-( 1,2-dicyclopentenyl)rhodacarborane complexes with the agostic C--H...Rh bond were synthesized starting from mono- C-substituted anionic nido-carboranes [ nido-7-R-7,8-C 2B 9H 11] –. The resulting diastereomeric mixtures were separated into individual isomers by either crystallization or chromatography. The structures and the stereochemistry of the diastereomeric complexes were studied in detail by 1H and 13C NMR spectroscopy. The relative configurations of two key isomers were established by X-ray diffraction analysis. The mechanism of the stereospecific formation of diastereomeric complexes is discussed. 相似文献
6.
Summary [Fe 2( -Cp) 2(CNAr) 4] (2) (540-01, C 6H 4Me-2, C 6H 4Et-2, C 6H 3Me 2-2,4, C 6H 3Me 2-2,6, C 6H 3(Me)Et-2,6, C 6H 3Et 2-2,6 or C 6H 3
i-Pr 2-2,6) react with I 2 to give [Fe( -Cp)(CNAr) 2I], but with Br 2[Fe( -Cp) (CNAr) 3] + salts are the only products; IBr gives a mixture of the two. With SnX 2 (X = F, Cl, Br or I) in refluxing n-butanol, (2) gives isolable [{Fe( -Cp)(CNAr) 2} 2SnX 2] only when the CNAr ligands have two ortho substituents, otherwise decomposition occurred. When X = F, [Fe( -Cp) (CNAr) 2SnF 3] was also obtained from this reaction. Attempts to prepare [Fe( -Cp)(CNAr) 2X] (X = Cl or Br) by reaction of (2) with HX in the presence of air gave rather unstable products which with SnX 2 formed [Fe( -C 5H 5)-(CNAr) 2SnX 3]. Similar compounds, [Fe( -Cp) (CNAr) 2 SnX 2I], were obtained from [Fe( -Cp)-(CNAr) 2I] and SnX 2 (X = Cl or Br but not I). All of these complexes are much less stable than their Fe( -Cp)(CO) 2 counterparts; all decompose in solution to [Fe( -Cp)(CNAr) 3] + which then break down to unidentified species. X-ray diffraction studies show that in [Fe( -Cp)(CNC 6H 3- i-Pr 2-2,6) 2I] and [{Fe( -Cp)(CNC 6H 3Me 2-2,6) 2} 2SnBr 2] there is pseudo-octahedral coordination about Fe. In the latter there is also distorted tetrahedral coordination about Sn so that its structure is very similar to that of [{Fe( -Cp)(CO) 2} 2SnCl 2]. Spectroscopic studies show that in all complexes rotation of the aryl rings of the CNAr ligands cannot be slowed in solution, and that there is free rotation about all 540-02 bonds. 相似文献
7.
The reactions of a complex [( 4-C 7H 8)RhCl] 2 (C 7H 8 is norbornadiene) with salts of substituted nido-dicarbaundecaborates, [K][ nido-7-R 1-8-R 2-7,8-C 2B 9H 10] (R 1 = R 2 = H ( a); R 1 = R 2 = Me ( b); R 1, R 2 = 1,2-(CH 2) 2C 6H 4 ( c); R 1 = Me, R 2 = Ph ( d)), in CH 2Cl 2 afforded new closo-( 2, 3-(4-vinylcyclopenten-3-yl))rhodacarboranes. The structures of the compounds were studied by multinuclear NMR spectroscopy. A probable mechanism of the rearrangement of the norbornadiene ligand is discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1875–1878, September, 2004. 相似文献
8.
Binuclear Rh III and Ru II complexes of the [M 1-CN-M 2] +BF
4
–
(M 1 and/or M 2 are ( 5-Cp)( 3-C 3H 5)Rh and ( 6-C 6H 6)( 3-C 3H 5)Ru) type, heteronuclear organometallic compound ( 5-Cp)( 3-C 3H 5)RhCNPd( 3-C 3H 5)Cl, and mononuclear Rh III and Ru II complexes [( 3-C 3H 5)LM(MeCN)] +
BF4
–
(M = Rh, L = 5-Cp; M = Ru, L = 6-C 6H 6) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [( 5-Cp)( 3-C 3H 5)Rh(MeCN)] +
BF4
–
with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995. 相似文献
9.
The ruthenium arene complexes [(-arene)Ru(-9-SMe 2-7,8-C 2B 9H 10)] + (arene = C 6H 6 ( 3a); arene = 1,3,5-C 6H 3Me 3 ( 3b)) with the monoanionic carborane ligand were synthesized by the reactions of the [9-SMe 2-7,8-C 2B 9H 10] – anion with [(-arene)RuCl 2] 2. The structure of the compound [ 3a]BPh 4 was established by single-crystal X-ray diffraction analysis. 相似文献
10.
Summary [RuCl 2(CO) 2]
n
reacts with the Schiff base 1-acetylferrocenethiosemicarbazone, [Fe( -Cp)( -C 5H 4MeC=NN-HCSNH 2)] to give [Fe( -Cp)( -C 5H 4MeC=NN-HCSNH 2)RuCl 2(CO) 2] and with 1-acetylferrocenesemicarbazone [Fe( -Cp)( -C 5H 4MeC=NN-HCSNH 2)] to give [Fe( -Cp)( -C 5H 4MeC=NN-HCSNH 2)RuCl 2-(CO) 2]. Spectroscopic data indicate that the Schiff bases act as bidentate ligands and coordinate to ruthenium via the hydrazinic N and either the S or O atoms, respectively, giving stable heterobimetallic complexes, which have been characterized by i.r. and 1H-n.m.r. spectroscopies, and elemental analyses.Part of this work was presented at the First International Conference in Chemistry and its applications in Doha, Qatar, 1993. 相似文献
11.
The reactions of polynuclear cobalt(ii) trimethylacetates [Co(OH)
n
(OOCCMe 3) 2–n
]
x
, Co 6( 3-OH) 2(OOCCMe 3) 10(HOOCCMe 3) 4, or Co 4( 3-OH) 2(OOCCMe 3) 6(HOEt) 6 with an excess of N-phenyl- o-phenylenediamine ( 1) in toluene followed by treatment with atmospheric oxygen afforded the diamagnetic complex [Co{ 2-(NPh)(NH)C 6H 4} 2{ 1-(NH 2)C 6H 4(NPhH)}] +(Me 3CCOO...H...OOCCMe 3) – ( 3), whose cation contains the Co III atom. The reaction of Co 4( 3-OH) 2(OOCCMe 3) 6(HOEt) 6 with a deficient amount of diamine 1 in acetonitrile under an argon atmosphere gave rise to the antiferromagnetic ionic complex [Co{ 2-(NPh)(NH)C 6H 4} 2MeCN] +[Co 2( 2, 2-OOCCMe 3)( 2-OOCCMe 3) 2( 2-OOCCMe 3) 2] –·2MeCN ( 4), whose cation is an isoelectronic analog of the cation in complex 3. The structures of the new compounds were established by X-ray diffraction analysis. 相似文献
12.
New cationic complexes [( 6-C 13H 10)Fe( 5-Cp *)]PF 6 and [( 6-9-CH 3-C 13H 9)Fe( 5-Cp *)]PF 6 were obtained by the reaction of Cp *Fe(CO) 2Br with fluorene and 9-methylfluorene, respectively. Deprotonation of these complexes by t-BuOK in THF affords zwitter-ionic compounds ( 6-C 13H 9)Fe( 5-Cp *) and ( 6-9-CH 3-C 13H 8)Fe( 5-Cp *) ( A). When A is heated in nonane at 150 °C it undergoes 65 inter-ring rearrangement with the formation of hexamethyldibenzoferrocene ( B). The electrochemical behavior of A and B was studied by cyclic voltammetry. One-electron reduction of A and B to the corresponding radical anions induces inter-ring haptotropic rearrangement A
.–B
.–. The equilibrium in the 19 state is shifted to the 6-isomeric radical anion A
.–, while in the 18 precursors, it shifts to the 5-isomer B.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 319–324, February, 1994.The authors are grateful to D. V. Zagorevskii (A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences) for recording and interpreting the mass spectra, and to A. A. Borisenko (Moscow State University) for recording the NMR spectra.This work was financially supported by the Russian Foundation for Basic Research (Grant 93-03-5209). 相似文献
13.
Rhodacarboranes closo-3,3-(Ph 3P) 2-3-H-3,1,2-RhC 2B 9H 11 and closo-( 2, 3-C 7H 7CH 2)-3,1,2-RhC 2B 9H 11 are catalysts for the alcoholysis of hydridesilanes. Closo-3,3-( 2, 3-C 7H 7CH 2)-3,1,2-RhC 2B 9H 11 displays greater activity than closo-3,3-(Ph 3P) 2-3-H-3,1,2-RhC 2B 9H 11 though both rhodacarboranes catalyze the alcoholysis of hydridesilanes more efficiently than (Ph 3P) 3RhCl.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1657–1660, July, 1992. 相似文献
14.
Chelate exo- nido-ruthenacarboranes exo-5,6,10-[RuCl(Ph 2P(CH 2) 4PPh 2)]-5,6,10-(μ-H) 3-10-H-7,8-R,R′- nido-7,8-C 2B 9H 6 (R, R′ = H, PhCH 2) were synthesized by the direct method using the reaction of Cl 2Ru(PPh 3)(Ph 2P(CH 2) 4PPh 2) with [7,8-R,R′- nido-7,8-C 2B 9H 10][K] in benzene. Unsubstituted exo-nido-ruthenacarborane (R, R′ = H) was used in situ for the synthesis of the dinuclear Ru-Cu exo-closo cluster of the formula exo-closo-(Ph 3P)Cu(μ-H)Ru(Ph 2P(CH 2) 4PPh 2)(η 5-C 2B 9H 11). The isomerism of the complex and the crystal structure were studied by NMR spectroscopy and X-ray diffraction. The catalytic activity of the cluster in the atom transfer radical polymerization of methyl methacrylate was investigated. 相似文献
15.
ansa-Metallocenes ( 5: 5-C 24H 16)M(THF) 2 (M = Sm ( 1), Yb ( 2), Ca ( 3)) and ( 5: 5-C 24H 16)MI(THF) (M = Dy ( 8), Er ( 9), Tm ( 10), Lu ( 11)) were prepared in 50—90% yields by the in situ reactions of two equivalents of potassium acenaphthylenide K +C 12H 8
– with MI 2 or MI 3, respectively. Complexes 2 and 3 were also obtained by direct reduction of acenaphthylene with ytterbium and calcium naphthalenides, respectively. An ESR signal of the acenaphthylene radical anion, which was observed upon dissolution of compound 2 in THF, indicates that the [C 24H 16] 2–
ansa-ligand dissociated into two [C 12H 8] ·– radical anions. Hydrolysis of complex 2 in benzene afforded 1,1",3,3"-tetrahydro-3,3"-biacenaphthylene ( 4) and 3,3",4,4"-tetrahydro-3,3"-biacenaphthylene ( 5). The reaction of complex 2 with ZrCl 4 and the reaction of compound 3 with Me 3SiCl proceeded with the cleavage of the C—C bond between two acenaphthylene fragments of the [C 24H 16] 2–
ansa-ligand to produce ( 2-C 12H 8)ZrCl 2(THF) 3 ( 6) and bis(trimethylsilyl)acenaphthene (Me 3Si) 2C 12H 8 ( 7), respectively. Compounds 1—3, 6, 7, and 11 were characterized by 1H and 13C NMR spectroscopy. The temperature dependence of the 1H NMR spectrum of compound 11 in tetrahydrofuran is indicative of the dynamic exchange of the solvent molecules in the coordination sphere of the Lu atom. After cooling of the solution to 210 K, the dynamic process was terminated as evidenced by the nonequivalence of the 1H signals of two acenaphthylene fragments. According to the X-ray diffraction data for complex 11, dimerization of two acenaphthylene radical anions at the Lu atom gave rise to the rac-ansa-metallocene structure. In compound 11, the Lu atom is 5-coordinated by two five-membered rings of the acenaphthylene ligands and also by the I atom and the THF molecule. The coordination environment about the Lu atom is a distorted tetrahedron. The average distance between the lutetium atom and the carbon atoms of the five-membered rings is 2.623 . 相似文献
16.
The reaction of the dinuclear complex Co 2(-OOCCMe 3) 2( 2-OOCCMe 3) 2bpy 2 ( 1) with the polymer [Co(OH)
n
(OOCCMe 3) 2–n
]
x
afforded the unsymmetrical dinuclear complex bpyCo 2( 2- O, 2-OOCCMe 3)( 2- O, O"-OOCCMe 3) 2( 2-OOCCMe 3) ( 2). The reaction of 2,2"-dipyridylamine with [Co(OH)
n
(OOCCMe 3) 2–n
]
x
gave rise to the analogous complex [(C 5H 4N) 2NH]Co 2( 2- O, 2-OOCCMe 3)(-OOCCMe 3) 2( 2-OOCCMe 3) ( 3). The reaction of complex 1 with Ni 4( 3-OH) 2(-OOCCMe 3) 4(OOCCMe 3) 2(MeCN) 2[ 2- o-C 6H 4(NH 2)(NHPh)] 2 ( 4) produced an isostructural heterometallic analog of complex 2 with composition bpyM 2( 2- O, 2-OOCCMe 3)( 2- O, O"-OOCCMe 3) 2( 2-OOCCMe 3) ( 5) (M = Co, Ni; Co : Ni = 1 : 1) and the dinuclear heterometallic complex bpy(HOOCCMe 3)M(-OH 2)(-OOCCMe 3) 2M(OOCCMe 3) 2[ o-C 6H 4(NH 2)(NHPh)] ( 6) (M = Co, Ni; Co : Ni = 0.15 : 1.85). Compounds 2 and 5 exhibit ferromagnetic spin-spin exchange interactions. 相似文献
17.
The oxidation of the carbon-centered [( 6-C 13H 9)Cr(CO) 3] – anion ( 1
–) results in formation of (- 6: 6-9,9-bifluorenyl)bis-chromiumtricarbonyl ( 3) due to coupling of the intermediate carbon-centered radical (1 .). The oxidation of the metal-centered anion [( 5-C 13H 9)Cr(CO) 3] – ( 2
–), which is isomeric to the 1 – anion, gives an equilibrium mixture of the chromium-centered radical {( 5-C 13H 9)Cr(CO) 3} . ( 2
.) and its dimer [( 5-C 13H 9)Cr(CO) 3] 2 ( 6). Radical 2
. readily reacts with MeI and the solvent (THF); the resulting derivatives, ( 5-C 13H 9)Cr(CO) 3R (R=Me ( 10); R=H ( 7)), undergo fast ricochet inter-ring 56 rearrangements into ( 6-9R-C 13H 9)Cr(CO) 3 (R=CH 3 ( 9); R=H ( 4)).Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1354–1358, July, 1995.The authors are grateful to D. V. Zagorevskii who recorded the mass spectra. This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-05209) and the International Science Foundation (Grant Nos. MQ 4000 and REV 000). 相似文献
18.
The roe of oxidatively induced homolyhc scission a the C(sp 3)-H bonds in the iron phenykychhexadienyl complexes Fe( 5-6-PhC 6H 6)( 5-C 5H 5) (1) depends on the spatial orientation of the Ph substitutent. In the case of the ( 1
endo
+) radical cation this process, resulting in the cationic biphenyl complex (Fe( 6 -C 6H 5C 6H 5)( 5-C 5H 5)] + ( 2
+), is fast and proceeds for several minutes. In the case of the more stable radical cation ( 1
exo
+) the formation of 2 + is slow and takes tens minutes to complete.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1698–1700, July, 1996. 相似文献
19.
Summary The tetramethyldisiloxane-bridged hafnocene complex [HfCl 2{-( 5-C 5H 4)SiMe 2OSiMe 2( 2-C 5H 4)}] ( 1) has been prepared by the reaction of HfCl 4 with the dilithiated bis(cyclopentadienyl)disiloxane (LiC 5H 4SiMe 2) 2O in a molar ratio of 1:2. The new compound was characterized by spectroscopic and X-ray diffraction methods. The crystals are monoclinic of space group P2 1/c and isostructural with the corresponding complexes of titanium and zirconium. The unit cell dimensions are a=13.51(1) Å, b=8.672(7) Å, c=15.41(1) Å, =97.15(2)°, and Z=4.
Darstellung und Röntgenkristallstruktur von [1,3-Bis(5-cyclopentadienyl)-1,1,3,3-tetramethyldisiloxan]hafnium(IV)dichlorid Zusammenfassung Der tetramethyldisiloxan-überbrückte Hafnocenkomplex [HfCl2{-(5-C5H4)-SiMe2OSiMe2(2-C5H4)}] (1) wurde durch Umsetzung von HfCl4 mit dem lithiiertenBis(cyclopentadienyl)disiloxan (LiC5H4SiMe2)2O im Molverhältnis 1:2 dargestellt. Die neue Verbindung wurde spektroskopisch und röntgenographisch charakterisiert. Sie kristallisiert in der monoklinen RaumgruppeP21/c und ist isostrukturell mit den entsprechenden Titan-und Zirkoniumkomplexen. Die Dimensionen der Einheitszelle sinda=13.51(1) Å,b=8.672(7) Å,c=15.41(1) Å, =97.15(2)° undZ=4. 相似文献
20.
Ruthenium(ii) and (iii) carborane complexes containing XantPhos as a ligand were synthesized for the first time. It was shown that the reaction of the known complex exo-5,6,10-[Cl(Ph3P)2Ru]-5,6,10-(µ-H)3-10-H-nido-7,8-C2B9H8 with a 10% molar excess of XantPhos in benzene at 80 °C leads to a new closo-ruthenacarborane 3-Cl-3,3-[x2-XantPhos]-closo-3,1,2-RuC2B9H11, which can be easily converted to the corresponding acetonitrile complex 3-CH3CN-3,3-[x2-XantPhos]-closo-3,1,2-RuC2B9H11 by the reaction with isopropylamine in a dichloromethane—acetonitrile solvent mixture at 40 °C. These compounds, as well as previously synthesized ruthenium(ii) carborane complexes, were used as a basis for new catalyst systems allowing to conduct controlled radical polymerization at high rates even at low catalyst loading. The specific features of methyl methacrylate polymerization under the action of the indicated catalyst systems were considered and the mechanism of the process was investigated. 相似文献
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