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1.
The reaction of [C5H4(CH2)nX]Tl (1: n = 2, X = NMe2, OMe, CN; n = 3, X = NMe2) with [(η6-C6H6)RuCl(μ-Cl)]2, 2, afforded the sandwich compounds [{η5-C5H4(CH2)nX}Ru(η6-C6H6)]PF6, 3, and [η5-C5H4(CH2)nX]2Ru, 4. Photolytic cleavage of 3 in acetonitrile afforded the tethered products [{η5:κN-C5H4(CH2)nX}Ru(CH3CN)2]PF6, 5. 相似文献
2.
A series of water soluble complexes of general formula [(η6-arene)Ru{(C5H4N)2CNRi}Cl]PF6 have been prepared by the reaction of [{(η6-arene)RuCl2}2] with appropriate 2,2′-dipyridyl-N-alkylimine ligands (dpNRi) in the presence of NH4PF6 (where; R = Me or Et; arene = p-cymene, C6Me6, C6H6). The 2,2′-dipyridyl-N-alkylimine ligands are prepared by reaction of 2,2′-dipyridyl ketone with the corresponding alkylamine. The complexes are readily obtained as air stable yellow to dark brown solids by simple stirring at room temperature. The complexes are isolated as their hexafluorophosphate salts and characterized on the basis of spectroscopic data. The molecular structure of representative complex [(η6-C6Me6)Ru{(C5H4N)2CN-Me}Cl]PF6 has been determined by single crystal X-ray diffraction studies. 相似文献
3.
The dinuclear complex [(η6-C6H6)Ru(μ-N3)Cl]2 (1) is obtained by the reaction of [(η6-C6H6)RuCl2]2 with sodium azide in ethanol. The benzene ruthenium β-diketonato complexes of the general formula [(η6-C6H6)Ru(L∩L)Cl] {L∩L = O,O′-acac (2); O,O′-bzac (3); O,O′-dbzm (4)} are obtained in methanol by the reaction of [(η6-C6H6)RuCl2]2 with the corresponding β-diketonates. These complexes further react with sodium azide in ethanol to yield complexes of the type [(η6-C6H6)Ru(L∩L)N3] [L∩L = O,O′-acac (5); L∩L = O,O′-bzac (6); L∩L = O,O′-dbzm (7)]. The complexes 5-7 are obtained as well by treating 1 with sodium salts of β-diketonates. These neutral benzene ruthenium azido complexes undergo [3+2] dipolar cycloaddition reaction with activated alkynes (MeO2CCCCO2Me, EtO2CCCCO2Et) or fumaronitrile (NCHCCHCN) to yield the corresponding benzene ruthenium triazolato complexes; [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Me)2}] (8), [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Et)2}] (9), [(η6-C6H6)Ru(O,O′-acac){N3C2HCN}] (10), [(η6-C6H6)Ru(O,O′-bzac){N3C2HCN}] (11) and [(η6-C6H6)Ru(O,O′-dbzm){N3C2HCN}] (12). These complexes are fully characterized on the basis of microanalyses, FT-IR and FT-NMR spectroscopy. The molecular structure of [(η6-C6H6)Ru(O,O′- acac){N3C2(CO2C2H5)2}] (9) is confirmed by single crystal X-ray diffraction study. 相似文献
4.
Guang Zhu 《Inorganica chimica acta》2008,361(11):3221-3229
The reactivity of Mo(PMe3)6 towards 6-membered heterocyclic aromatic nitrogen compounds, namely pyridine, pyrazine, pyrimidine and triazine, has been investigated as part of an effort to define the coordination chemistry of molybdenum relevant to hydrodenitrogenation. For example, Mo(PMe3)6 reacts with pyridine to yield initially (η2-N,C-pyridyl)Mo(PMe3)4H, an uncommon example of an η2-pyridyl-hydride complex. The formation of (η2-N,C-pyridyl)Mo(PMe3)4H is reversible and treatment with PMe3 regenerates Mo(PMe3)6 and pyridine. At elevated temperatures, (η2-N,C-pyridyl)Mo(PMe3)4H dissociates PMe3 and converts to the η6-pyridine complex (η6-pyridine)Mo(PMe3)3. Pyrazine, pyrimidine and 1,3,5-triazine likewise react with Mo(PMe3)6 to yield (η2-N,C-pyrazinyl)Mo(PMe3)4H, (η2-N,C-pyrimidinyl)Mo(PMe3)4H and (η2-N,C-triazinyl)Mo(PMe3)4H, respectively. At elevated temperatures (η2-N,C-pyrazinyl)Mo(PMe3)4H and (η2-N,C-pyrimidinyl)Mo(PMe3)4H dissociate PMe3 and convert to (η6-pyrazine)Mo(PMe3)3 and (η6-pyrimidine)Mo(PMe3)3 in which the heterocycle coordinates to molybdenum in an unprecedented η6-manner. 相似文献
5.
Substitution reaction of chloro η6-arene ruthenium N∩O-base complexes [(η6-arene)Ru(N∩O)Cl] [N∩O = pyrazine-2-carboxylic acid (pca-H), 8-hydroxyquinoline (hq-H); arene = p-iPrC6H4Me, N∩O = hq (1); arene = C6Me6, N∩O = hq (2)] with NaN3 yield the neutral arene ruthenium azido complexes of the general formula [(η6-arene)Ru(N∩O)N3] [N∩O = pca, arene = p-iPrC6H4Me (3), arene = C6Me6 (4); N∩O = hq, arene = p-iPrC6H4Me (5), arene = C6Me6 (6)]. These complexes undergo [3 + 2] dipolar cycloaddition reaction with activated alkynes dimethyl and diethyl acetylenedicarboxylates to yield the arene triazole complexes [(η6-arene)Ru(N∩O){N3C2(CO2R)2}] [N∩O = pca, R = Me, arene = p-iPrC6H4Me (7), C6Me6 (8); R = Et, arene = p-iPrC6H4Me (9), C6Me6 (10); N∩O = hq, R = Me, arene = p-iPrC6H4Me (11) C6Me6 (12); R = Et, arene = p-iPrC6H4Me (13), C6Me6 (14)]. On the bases of proton NMR study, in the above triazole complexes N(2) isomers are assigned with dimethylacetylenedicarboxylate whereas N(1) isomers with diethylacetylenedicarboxylate. All complexes have been characterized by IR and NMR spectroscopy as well as by elemental analysis. The molecular structures of the azido complexes [(η6-p-iPrC6H4Me)Ru(pca)N3] (3), [(η6-p-iPrC6H4Me)Ru(hq)N3] (5) and [(η6-C6Me6)Ru(hq)N3] (6) have been established by single crystal X-ray diffraction studies. 相似文献
6.
Robert J. Baker 《Inorganica chimica acta》2006,359(15):4797-4801
The reaction of [(η7-C7H7)Zr(η5-C5H5)] with two Lewis bases, tetramethylimidazolin-2-ylidene and PMe3, is reported and their stability probed via spectroscopic and theoretical methods. The strongly σ-basic N-heterocyclic carbene forms a stable adduct which has been structurally characterised, whilst the PMe3 ligand coordinates weakly to the metal centre. Variable temperature 31P NMR spectroscopy has been used to determine the activation energy for this process (ΔG‡ = 40.5 ± 1.9 kJ mol−1). DFT calculations have been performed on both complexes and the structures discussed. In addition, the enthalpies for the formation of these compounds have been calculated [ΔH0(Zr-IMe) = −56.3 kJ mol−1; ΔH0(Zr-PMe3) = −2.3 kJ mol−1] and show that the N-heterocyclic carbene forms a thermodynamically much more stable adduct than that with PMe3. 相似文献
7.
Konstantis F. Konidaris Eugenia Katsoulakou Vassilis Psycharis Theocharis C. Stamatatos Evy Manessi-Zoupa 《Inorganica chimica acta》2011,376(1):470-478
The first employment of pyridine-2-amidoxime [(py)C(NH2)NOH] in zinc(II) chemistry is reported. The syntheses, crystal structures, and spectroscopic characterization are described for complexes [Zn(O2CR)2{(py)C(NH2)NOH}2] (R = Me; 1, Ph; 2), [Zn2(acac)2{(py)C(NH2)NO}2] (3), and [Zn(NO3){(py)C(NH2)NOH}2](NO3) (4). The reactions between Zn(O2CR)2·2H2O (R = Me, Ph) or Zn(NO3)2·5H2O and two equivalents of (py)C(NH2)NOH in MeOH led to mononuclear compounds 1, 2 and 4, respectively. All three complexes contain two neutral N,N′-chelating (η2) (py)C(NH2)NOH ligands, coordinated through the Npyridyl and Noxime atoms. In contrast, the use of Zn(acac)2·H2O in place of Zn(O2CR)2·2H2O gives the dinuclear compound 3, which instead contains the anionic, η1:η1:η1:μ bridging form of the organic ligand; the ZnII atoms are doubly bridged by the diatomic oximate groups of the (py)C(NH2)NO− groups. Strong intra- and intermolecular hydrogen bonding interactions provide appreciable thermodynamic stability and interesting supramolecular chemistry for compounds 1-4. The photoluminescence properties of complexes 1-4 recorded in the solid state at room temperature are also presented. 相似文献
8.
Elia Tfouni Antônio Marcos de Souza Macêdo Kleber Queiroz Ferreira Zênis Novais da Rocha 《Inorganica chimica acta》2005,358(10):2909-2920
The spectral (UV-Vis and IR) and electrochemical behavior of the nitrile bonded complexes [Ru(NH3)5L]2+ (L = 1,4-dicyanobenzene (1,4-dcb), 1,2-dicyanobenzene (1,2-dcb)), [Ru(NH3)5(NHC(OH)-bz-4-CN)]3+, [Ru(NH3)5(NHC(O)-bz-2-CN)]2+ and [Ru(NH3)5(NH(C)NHC(O)bz)]3+ (NH(C)NHC(O)-bz = 3-imino-1-oxo-isoindoline) are described. Oxidation of [Ru(NH3)5L]2+, at 0 ? pH ? 6, is followed by hydrolysis of the coordinated nitrile to give amide complexes in which the amide is through the nitrogen, with pH-dependent rate constants. The estimated values of the rate constant of hydrolysis (kobs) at 25 °C are 2.9 × 10−3 s−1 for [Ru(NH3)5(1,4-dcb)]3+ and 5.6 × 10−3 s−1 for [Ru(NH3)5(1,2-dcb)]3+ at pH 4.65. Reduction of [Ru(NH3)5(NHC(O)-bz-4-CN)]2+ and [Ru(NH3)5(NHC(O)-bz-2-CN)]2+ is followed by two reactions, one is an aquation forming [Ru(NH3)5(OH2)]2+ and free ligand, and the other an intramolecular linkage isomerization forming [Ru(NH3)5(NC-bz-4-NH2C(O))]2+ and [Ru(NH3)5(NC-bz-2-NH2C(O))]2+. The oxidized1,2-cyanobenzamide complex [Ru(NH3)5(NHC(OH)-bz-2-CN)]3+ undergoes an amide to nitrile intramolecular linkage isomerization, followed by a cyclization reaction resulting in [Ru(NH3)5(NH-(C)(HN-C(O)-2-bz))]3+ ((NH-(C)(HN-C(O)-2-bz)) = 3-imino-1-oxo-isoindoline bonded through the exocyclic nitrogen) (pKa = 4.3). The rates of these reactions, which occur with neighboring group participation, increase with acidity. The reduced form, [Ru(NH3)5(NH-(C)(HN-C(O)-2-bz))]2+, is relatively substitution inert. 相似文献
9.
Salvador Conejero 《Inorganica chimica acta》2009,362(12):4539-172
The synthesis of a series of rhodium and iridium complexes bearing bulky cyclopentadienyl or hydro(trispyrazolyl)borate ligands is described. The rhodium cyclopentadienyl and hydrotris(pyrazolyl)borate diene compounds, [(η5-C5Me4But)Rh(η4-2,3-MeRC4H4] (R = H, 1; Me, 2) and TpMsRh(η4-2,3-MeRC4H4) (R = H, 3; Me, 4; TpMs is hydrotris(3-mesitylpyrazol-1-yl)borate), respectively, have been prepared from the corresponding Rh(I) diene precursors and Zn(C5Me4But)2 (for 1 and 2), or TlTpMs (for 3 and 4), as effective C5Me4But or TpMs transfer reagents. In contrast with these results, attempts to obtain a bis(ethylene) derivative of the TptolIr(I) unit (Tptol stands for hydrotris(3-p-tolylpyrazol-1-yl)borate) have provided instead the Ir(III) complex [(κ4-N,N′,N″,C-Tptol)-Ir(C2H5)(C2H4)] (5), whose formation requires C-H bond activation of a molecule of ethylene and of one of the Tptolp-tolyl substituents. In refluxing toluene 5 experiences metalation of a second p-tolyl substituent to give [(κ5-N,N′,N″,C,C′-Tptol)-Ir(C2H4)] (6), which features unusual κ5-Tptol coordination. The latter compound reacts with carbon monoxide to yield the corresponding carbonyl, 7. 相似文献
10.
Ring coupled bimetallic derivatives (μ-η5:5-C5H4C5H4)[Nb(CO)4]2 and [μ-CH2(η5-C5H4)2][M(CO)4]2, where M = Nb and Ta have been prepared. The molecular structures of the latter two compounds have been determined: , triclinic, , a = 8.028(2) Å, b = 11.414(1) Å, c = 12.711(2) Å, α = 75.020(8)°, β = 80.34(2)°, γ = 79.46(2)°, V = 1097.3(4) Å3, Z = 2, R(F) = 2.79%; [μ-CH2(η5-C5H4)2][Ta(CO)4]2, triclinic, , a = 7.815(3) Å, b = 10.275(4) Å, c = 13.135(4) Å, α = 104.25(3)°, β = 100.26(4)°, γ = 96.86(3)°, V = 991.2(6) Å3, Z = 2, R(F) = 3.00%. 相似文献
11.
Complexes of the type (η4-BuC5H5)Fe(CO)2(P) (P = PPh2Py 3, PPhPy24, PPy35; Py = 2-pyridyl) were satisfactorily prepared. Upon treatment of 3 with M(CO)3(EtCN)3 (M = Mo, 6a; W, 6b), the pyridyl N-atom could be coordinated to the metal M, which then eliminates a CO ligand from the Fe-centre and induced an oxidative addition of the endo-C-H of (η4-BuC5H5). This results in a bridged hydrido heterodimetallic complex [(η5-BuC5H4)Fe(CO)(μ-P,N-PPh2Py)(μ-H)M(CO)4] (M = Mo, 7a, 81%; W, 7b, 76%). The reaction of 4 or 5 with 6a,b did not give the induced oxidative addition, although these complexes contain more than one pyridyl N-atom. The reaction of 4 with M(CO)4(EtCN)2 (M = Mo, 9a; W, 9b) produced heterodimetallic complexes [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′-PPhPy2)M(CO)4] (M = Mo, 10a, 81%; W, 10b, 83%). Treatment of 5 with 6a,b gave [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′,N″-PPy3)M(CO)3] (M = Mo, 12a, 96%; W, 12b, 78%). 相似文献
12.
The haptotropic migration of Fe from the unsubstituted ring to the substituted one in the pentalenic complexes [CpFe(η5-1,3 C8H4R2)]q (q = +1, 0, −1) has been investigated by the means of DFT calculations in the case of R = H, CH3, NH2, CF3 and CN. The low energy pathway is a least-motion one-step process in the cationic case. In the anionic series, it is a two-step process involving an intermediate in which the metal moiety is η3-bonded in an exocyclic way to the pentalene ligand. The activation barriers and the preference for the Fe coordination on one ring rather on the other one is investigated with respect to the donor or acceptor abilities of R. The effect of changing q on the haptotropic situation is analyzed in terms of redox molecular switching. 相似文献
13.
A series of tridentate ligands consisting of mixed aromatic and aliphatic amine derivatives of single amino acid chelates and phenylpiperazine have been developed, and their reactions with [NEt4]2[ReBr3(CO)3] have been investigated. The compounds [Re(CO)3{(NC5H4CH2)NCH3(C2H4)NHCH3}]Br (4), [Re(CO)3{(NC5H4CH2)NCH3(C2H4)NCH3(CH2)xCOOC2H5}]Br (x = 1, 5; x = 4, 6) [Re(CO)3{(NC5H4CH2)NH(C2H4)N(CH3)2}]Br (7), [Re(CO)3{(NC5H4CH2)N(CH 2COOC2H5)(C2H4)N(CH3)2}]Br (8) and [Re(CO)3(NC5H4CH2)(C2H4NH2)N(CH2)3-CH3Ophenpip]Br (9) (phenpip: phenylpiperazine, -C6H4-(CH2CH2)2N-) were prepared and characterized by elemental analysis, NMR, IR, HSMS and X-ray crystallography. All complexes exhibit fac-{Re(CO)3N3} coordination geometry in the cationic molecular unit. Crystal data for C13H17BrN3O3Re (4): orthorhombic, Pbca, a = 13.4510(8) Å, b = 10.5728(6) Å, c = 22.5378(13) Å, V = 3205.2(3) Å3, Z = 8; C17H23BrN3O5Re (5): orthorhombic, Pcca, a = 16.5907(7) Å,b = 14.8387(6) Å, c = 16.7075(7) Å, V = 4113.1(3) Å3, Z = 8; C13H25BrN3O7Re (7 · 4H2O): monoclinic, P21/n, a = 14.0698(17) Å, b = 9.6760(12) Å, c = 15.6099 (19) Å, β = 114.930(2)°, V = 1927.1(4) Å3, Z = 4; C17H23BrN3O5Re (8): monoclinic, P21/n, a = 7.5312(5) Å, b = 16.0366(10) Å, c = 16.8741(10) Å, β = 98.9990(10)°, V = 2012.9(2) Å3, Z = 4. 相似文献
14.
Two complexes containing o-ferrocenylbenzoate [o-−OOCH4C6Fc, Fc = (η5-C5H5)Fe(η5-C5H4)] components: {[Pb(η2-o-OOCH4C6Fc)2(phen)](NO3)} (phen = phenanthroline) (1) and {[Zn(η2-o-OOCH4C6Fc)2(bpe)](CH3OH)}n (bpe = 1,2-bis(4-pyridyl) ethene) (2) have been synthesized and structurally characterized by single crystal X-ray diffraction. 1 gives a discrete mononuclear framework, 2 features an infinite 1-D chain structure constructed by the bpe linking two adjacent zinc (II) ions. The third-order nonlinear optical (NLO) properties of complexes 1, 2 and the reactant o-NaOOCH4C6Fc were determined by Z-scan techniques in DMF solution. The results show that the structures of complexes have great impact on NLO properties. Complex 1 and o-NaOOCH4C6Fc display self-defocusing behaviors, while complex 2 exhibits strong self-focusing effect. The solution-state differential pulse voltammograms of complexes 1, 2 and o-NaOOCH4C6Fc were investigated as well. The results reveal that the half-wave potential of the ferrocenyl moieties is strongly influenced by the Pb(II) or Zn(II) ions in complexes 1 and 2. 相似文献
15.
M. Cristina Cassani 《Inorganica chimica acta》2005,358(5):1595-1604
The preparation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes is described. These are of formula [M{η5-C5H4(BX)}Cl3] [M = Ti and X = CAT (2a), CATt (2b) or CATtt (2c); X = CATtt and M = Zr (4a) or Hf (4b)], [M{η5-C5H4(BX)}2Cl2] [M = Zr, X = CAT (3a) or CATt (3c); or M = Hf, X = CAT (3b) or CATt (3d)], [M{(μ-η5-C5H3BCAT)2 SiMe2}Cl2] [M = Zr (5a) or Hf (5b)], [M{η5-C5H3(BCAT)2}Cl3] [M = Zr (6a) or Hf (6b)], [M{η5-C5H4BCAT}3(THF)] [M = La (7a), Ce (7b) or Yb (7c)], [Sn{η5-C5 H4(BCATt)}Cl](8) and [Fe{η5-C5H4(BCATt)}2] (9). The abbreviations refer to BO2C6H4-1,2 (BCAT) and the 4-But (BCATt) and the (BCATtt) analogues. The compounds 2a-9 have been characterised by microanalysis, multinuclear NMR and mass spectra. The single crystal X-ray structure of the lanthanum compound 7a is presented. 相似文献
16.
The reaction of the racemic chiral methyl complex (η5-C5H5)Re(NO)(PPh3)(CH3) (1) with CF3SO3H and then NH2CH2C6H5 gives [(η5-C5H5)Re(NO)(PPh3)(NH2CH2C6H5)]+ ([4a-H]+; 73%), and deprotonation with t-BuOK affords the amido complex (η5-C5H5)Re(NO)(PPh3)(NHCH2C6H5) (76%). Reactions of 1 with Ph3C+ X− and then primary or secondary amines give [(η5-C5H5)Re(NO)(PPh3)(CH2NHRR′)]+ X− ([6-H]+ X−; R/R′/X = a, H/NH2CH2C6H5/BF4; a′, H/NH2CH2C6H5/PF6; b, H/NH2CH2(CH2)2CH3/PF6; c, H/(S)-NH2CH(CH3)C6H5/BF4); d, CH2CH3/CH2CH3/PF6; e, CH2(CH2)2CH3/CH2(CH2)2CH3/PF6; f, CH2C6H5/CH2C6H5/PF6; g, -CH2(CH2)2CH2-/PF6; h, -CH2(CH2)3CH2-/PF6; i, CH3/CH2CH2OH/PF6 (62-99%). Deprotonations with t-BuOK afford the amines (η5-C5H5)Re(NO)(PPh3)(CH2NRR′) (6a-i; 99-40%), which are more stable and isolated in analytically pure form when R ≠ H. Enantiopure 1 is used to prepare (RReSC)-[6c-H]+, (RReSC)-6c, (S)-[6g-H]+, and (S)-6g. The crystal structures of [4a-H]+, a previously prepared NH2CH2Si(CH3)3 analog, [6a′,d,f,h-H]+, (RReSC)-6c, and 6f are determined and analyzed in detail, particularly with respect to cation/anion hydrogen bonding and conformation. In contrast to analogous rhenium containing phosphines, 6a-i show poor activities in reactions that are catalyzed by organic amines. 相似文献
17.
Maxim A. Ivanov Vladimir V. Sharutin Antonya P. Pakusina Willis Forsling 《Inorganica chimica acta》2007,360(9):2897-2904
O,O′-dipropyldithiophosphate and O,O′-di-iso-butyldithiophosphate (Dtph) tetraphenylantimony(V) complexes of the general formula [Sb(C6H5)4{S2P(OR)2}] (R = C3H7, i-C4H9) were prepared and studied by means of 13C, 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Distorted octahedral and trigonal bipyramidal molecular structures have been established for prepared complexes. These unexpected structural distinctions between chemically related compounds are defined by the principally different coordination modes of O,O′-dipropyldithiophosphate and O,O′-di-iso-butyldithiophosphate ligands in their molecular structures (i.e., S,S′-bidentate chelating and S-unidentately coordinated, respectively). To characterise quantitatively phosphorus sites in both species of dithiophosphate ligands, 31P chemical shift anisotropy parameters (δaniso and η) were calculated from spinning sideband manifolds in MAS NMR spectra. The 31P chemical shift tensors for the bidentate chelating and unidentately coordinated dithiophosphate ligands display a profoundly rhombic and nearly axially symmetric characters, respectively. 相似文献
18.
B-Chlorocatecholborane undergoes oxidative addition to M(PR3)3Cl (M = Rh, R = Me; M = Ir, R = Me, Et) yielding six-coordinate complexes of general formula mer,cis-(PR3)3Cl2M(BO2C6H4). The same M(PR3)3Cl complexes also react with B-bromocatecholborane to give a mixture of metal boryl homo- and heterodihalides (PR3)3X1X2M(BO2C6H4) (X1, X2 = Cl, Br), and the observed disproportionation is believed to involve the formation of a heteronuclear halide-bridged intermediate. The alkene 4-vinylanisole failed to react with the six-coordinate, 18-electron (PR3)3Cl2M(BO2C6H4) complexes at ambient temperatures. 相似文献
19.
Red or orange crystals of [Co(NH3)6]2Cl2[Fe(CN)6] · 4H2O (1), [Co(en)3]2Cl2[Fe(CN)6] · 2H2O (2) and [Co(en)3]4[Fe(CN)6]3 · 21.6H2O (3) were isolated from the aqueous systems Co3+-LN-[Fe(CN)6]4− (LN = NH3, en = 1,2-diaminoethane). In all isolated samples the combination of Mössbauer (δ values were from the range −0.07 to −0.08 mm/s) and IR spectra (ν(CN) stretching vibrations in the range 2015-2047 cm−1) confirms the presence of low spin Fe(II) in [Fe(CN)6]4− anions. X-ray structure analyses corroborate the ionic character of all studied compounds. These contain diamagnetic [Co(NH3)6]3+ (1) or [Co(en)3]3+ (2 and 3) complex cations and diamagnetic [Fe(CN)6]4− complex anions. In compounds 1 and 2 chloride anions are present, too. All three compounds contain water of crystallization, in compound 3 as many as 21.6 molecules per formula unit. 相似文献
20.
The 2-methallyl complex [(η5-C9H7)Ru(η3-2-MeC3H4)(PPh3)] (3), prepared from [(η5-C9H7)Ru(PPh3)2Cl] (2) and 2-MeC3H4MgCl, reacts with HX (X = Cl, CF3CO2) in the presence of ethene to give the chiral-at-metal compounds [(η5-C9H7)Ru(C2H4)(PPh3)X] (4, 5) in nearly quantitative yields. Treatment of 2 with AgPF6 and ethene affords [(η5-C9H7)Ru(C2H4)(PPh3)2]PF6 (6), which reacts with acetone to give the substitution product [(η5-C9H7)Ru(OCMe2)(PPh3)2]PF6 (7). The molecular structure of 7 has been determined crystallographically. Whereas treatment of 4 with CH(CO2Et)N2 yields the olefin complex [(η5-C9H7)Ru{η2-(Z)-C2H2(CO2Et)2}(PPh3)Cl] (8), the reactions of 4 and 5 with Ph2CN2, PhCHN2 and (Me3Si)CHN2 lead to the formation of the carbeneruthenium(II) derivatives [(η5-C9H7)Ru(CRR′)(PPh3)Cl] (9-11) and [(η5-C9H7)Ru(CRR′)(PPh3)(κ1-O2CCF3)] (12-14), respectively. Treatment of 9 (R = R′ = Ph), 10 (R = H, R′ = Ph) and 11 (R = H, R′ = SiMe3) with MeLi produces the hydrido(olefin) complexes [(η5-C9H7)RuH(η2-CH2CPh2)(PPh3)] (15), [(η5-C9H7)RuH(η2-CH2CHPh)(PPh3)] (18a,b) and [(η5-C9H7)RuH(η2-CH2CHSiMe3)(PPh3)] (19) via C-C coupling and β-hydride shift. The analogous reactions of 11 with PhLi gives the η3-benzyl compound [(η5-C9H7)Ru{η3-(Me3Si)CHC6H5}(PPh3)] (20). The η3-allyl complex [(η5-C9H7)Ru(η3-1-PhC3H4)(PPh3)] (17) was prepared from 10 and CH2CHMgBr by nucleophilic attack. 相似文献