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1.
Reactions of Cr(CO)3(η6-BT), in which the Cr is π-coordinated to the benzene ring of benzo[b]thiophene (BT), with Cp′(CO)2Re(THF), where Cp′ = η5-C5H5 or η5-C5Me5, give the products Cp′(CO)2Re(η2:η6-μ2-BT)Cr(CO)3 in which the Cr remains coordinated to the benzene ring and Re is bound to the C(2)=C(3) double bond. An X-ray diffraction study of Cp(CO)2Re(η2:η6-μ2-BT)Cr(CO)3 (3) provides details of the geometry. This structure contrasts with that of the Cp′(CO)2Re(BT) complexes that exist as mixtures of isomers in which the BT is coordinated to the Re through either the double bond (2,3-η2) or the sulfur (η1(S)). Thus, the electron-withdrawing Cr(CO)3 group in 3 stabilizes the 2,3-η2 mode of BT coordination to the Cp′(CO)2Re fragment. Implications of these results for catalytic hydrodesulfurization of BT are discussed. Crystal data for 3: triclinic, space group

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2.
Four complexes of the type [Cu4I4(CH3CN)2(L)2], L = aniline derivative: Cu4I4(CH3CN)2(2,6-dimethylaniline)2 (I), triclinic, , a = 12.449(3), B = 14.108(6), C = 10.606(4) Å, = 73.46(3), β = 95.00(2), γ = 73.42(3)°, V = 1682.3(10) Å3; Cu4I4(CH3CN)2(o-ethylaniline)2 (II), triclinic,

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, V = 1734.0(8) Å3; Cu4I4(CH3CN)2(6-ethyl-o-toluidine)2 (III), orthorhombic, Pnam, a = 14.976(6), b = 21.187(6), C = 12.545(2) Å, V = 3980.7(2) Å3; Cu4I4(CH3CN)2(p-anisidine)2 (IV), monoclinic, A2/a, A = 20.032(10), B = 7.863(1), C = 18.715(9) Å, β = 101.56(4)°, V = 2888.0(2) Å3; were examined by single crystal X-ray diffraction. Complexes I and II have no internal symmetry elements, III has an internal mirror and IV has a two-fold axis. Ab initio calculations based on the atomic positional parameters of complexes containing the three types of symmetry elements reveal HOMO orbitals to be dominated by the p orbitals of the iodine atoms whereas the LUMO orbitals contain major contributions from copper based p orbitals.  相似文献   

3.
Reaction of RuCl(η5-C5H5(pTol-DAB) with AgOTf (OTf = CF3SO3) in CH2Cl2 or THF and subsequent addition of L′ (L′ = ethene (a), dimethyl fumarate (b), fumaronitrile (c) or CO (d) led to the ionic complexes [Ru(η5-C5H5)(pTol-DAB)(L′)][OTf] 2a, 2b and 2d and [Ru(η5-C5H5)(pTol-DAB)(fumarontrile-N)][OTf] 5c. With the use of resonance Raman spectroscopy, the intense absorption bands of the complexes have been assigned to MLCT transitions to the iPr-DAB ligand. The X-ray structure determination of [Ru(η5-C5H5)(pTol-DAB)(η2-ethene)][CF3SO3] (2a) has been carried out. Crystal data for 2a: monoclinic, space group P21/n with A = 10.840(1), b = 16.639(1), C = 14.463(2) Å, β = 109.6(1)°, V = 2465.6(5) Å3, Z = 4. Complex 2a has a piano stool structure, with the Cp ring η5-bonded, the pTol-DAB ligand σN, σN′ bonded (Ru-N distances 2.052(4) and 2.055(4) Å), and the ethene η2-bonded to the ruthenium center (Ru-C distances 2.217(9) and 2.206(8) Å). The C = C bond of the ethene is almost coplanar with the plane of the Cp ring, and the angle between the plane of the Cp ring and the double of the ethene is 1.8(0.2)°. The reaction of [RuCl(η5-C5H5)(PPh)3 with AgOTf and ligands L′ = a and d led to [Ru(η5-C5H5)(PPh3)2(L′)]OTf] (3a) and (3d), respectively. By variable temperature NMR spectroscopy the rottional barrier of ethene (a), dimethyl fumarate (b and fumaronitrile (c) in complexes [Ru(η5-C5H5)(L2)(η2-alkene][OTf] with L2 = iPr-DAB (a, 1b, 1c), pTol-DAB (2a, 2b) and L = PPh3 (3a) was determined. For 1a, 1b and 2b the barrier is 41.5±0.5, 62±1 and 59±1 kJ mol−1, respectively. The intermediate exchange could not be reached for 1c, and the ΔG# was estimated to be at least 61 kJ mol−. For 2a and 3a the slow exchange could not be reached. The rotational barrier for 2a was estimated to be 40 kJ mol−. The rotational barier for methyl propiolate (HC≡CC(O)OCH3) (k) in complex [Ru(η5-C5H5)(iPr-DAB) η2-HC≡CC(O)OCH3)][OTf] (1k) is 45.3±0.2 kJ mol−1. The collected data show that the barrier of rotational of the alkene in complexes 1a, 2a, 1b, 2b and 1c does not correlate with the strength of the metal-alkene interaction in the ground state.  相似文献   

4.
Manganese tricarbonyl complexes (η5-C5H4CH2CH2Br)Mn(CO)3 (3) and (η5-C5H4CH2CH2I)Mn(CO)3 (4), with an alkyl halide side chain attached to the cyclopentadienyl ligand, were synthesized as possible precursors to chelated alkyl halide manganese complexes. Photolysis of 3 or 4 in toluene, hexane or acetone-d6 resulted in CO dissociation and intramolecular coordination of the alkyl halide to manganese to produce (η5:η1-C5H4CH2CH2Br)Mn(CO)2 (5) and (η5:η1-C5H4CH2CH2I)Mn(CO)2 (6). Low temperature NMR and IR spectroscopy established the structures of 5 and 6. Photolysis of 3 in a glass matrix at 91 K demonstrated CO release from manganese. Low temperature NMR spectroscopy established that the coordinated alkyl halide complexes are stable to approximately −20°C.  相似文献   

5.
The reactivity, towards nucleophiles and electrophiles, of dimolybdenum allenylidene complexes of the type [Cp2Mo2(CO)4(μ,η2(4e)-C=C=CR1R2)] (Cp=η5-C5H5) has been investigated. The nucleophilic attacks occur at the Cγ carbon atom, while electrophiles affec the C atom. Variable temperature solution 1H NMR studies show a dynamic behavior of these complexes consisting of an equilibrium between two enantiomers with a symmetrical [Cp2Mo2(CO)4(μ-σ,σ(2e)-C=C=CR1R2)] transition state. Extended Hückel MO calculations have been carried out on the model [Cp2Mo2(CO)4(μ,η2-C=C=CH2]. The calculated charges of the allenylidene carbon atoms suggest that the electrophilic attacks are under charge control, while the nucleophilic attacks are rather under orbital control.  相似文献   

6.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4.  相似文献   

7.
The reactions of [(H5C6)3P]2ReH6− with (CH3CN)3Cr(CO)3, (diglyme)Mo(CO)3 or (C3H7CN)3W(CO)3 led to the formation of [(H5C6)3P]2ReH6M(CO)3− (M = Cr, Mo, W) complexes. These have been characterized by IR and NMR spectroscopies, as well as elemental analyses. A single crystal X-ray diffraction study has also been carried out for the M = Cr complex as a K(18-crown-6)+ salt. The complex crystallizes as a THF monosolvate in the monoclinic space group P21/n with a = 22.323(6), B = 9.523(2), C = 27.502(5) Å, β = 104.98(2)0 and V = 5648 Å3 for Z = 4. The Re---Cr separation is 2.5745(12) Å, and the two phosphine ligands are oriented unsymmetrically. Although the hydride ligands were not found, the presence of three bridging hydrides and a dodecahedral coordination geometry about rhenium could be inferred. Low temperature 1H and 31P NMR spectroscopic studies did not reveal the low symmetry of the solid state structure.  相似文献   

8.
Metathesis of [(η3:η3−C10H16)Ru(Cl) (μ−Cl)]2 (1) with [R3P) (Cl)M(μ-Cl)]2 (M = Pd, Pt), [Me2NCH2C6H4Pd(μ-Cl)]2 and [(OC)2Rh(μ-Cl)]2 affords the heterobimetallic chloro bridged complexes (η3:η3-C10H16) (Cl)Ru(μ-Cl)2M(PR3)(Cl) (M = Pd, Pt), (η3:η3-C10H16) (Cl)Ru(μ-Cl)2PdC6H4CH2NMe2 and (η3:η3-C10H16) (Cl)Ru(μ-Cl)2Rh(CO)2, respectively. Complex 1 reacts with [Cp*M(Cl) (μ-Cl)]2 (M = Rh, Ir), [p-cymene Ru(Cl) (μ-Cl]2 and [(Cy3P)Cu(μ-Cl)]2 to give an equilibrium of the heterobimetallic complexes and of educts. The structures of (η3:η3-C10H16)Ru(μ-Cl)2Pd(PR3) (Cl) (R = Et, Bu) and of one diastereoisomer of (η3:η3-C10H16)Ru(μ-Cl)2IrCp*(Cl) were determined by X-ray diffraction.  相似文献   

9.
[Pt(COD)Cl2] (1) reacts with PPh2(C6H4COOH) (2a,b,c), PPh2(C6H4COONa) (2d), PPh(C6H4COOH)2 (4b,c) and P(C6H4COOH)3 (6b,c) with formation of the corresponding complexes [Pt(L)2Cl2] (3a,b,c,d, 5b,c, 7b,c). Halide abstraction from 3a by Ag+ promotes coordination of the ortho-carboxylate function to platinum, yielding [ -2)}{PPh2(C6H4COOH-2)}Cl] (bd8) and [ovbar|{PPh2(C6H4COO-2)}2] (bd9). Reaction of 1 with CO and 2a or 2b gives [Pt(CO)(L)Cl2] (10a,b), wherea 1 and 2,3-bis(diphenylphosphino) maleic anhydride yields

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(bd12) and [Pt{Ph2PC(COOH)=C(COOMe)-PPh2}Cl2] (13). The 1H, 13C and 31P NMR spectra are reported and discussed. The X-ray structural analysis of 3b showed the compound to be monoclinic, space group P21/n, Z=4, with a=1038.5(3), B=1792.6(4), C=2311.5(4) pm, β=91.6(2)° and Dcalc=1.353 g cm−3. The structure was solved from 4832 observed reflections with F0 > 4 σ(F0) and refined to a final R value of 0.0743. The Pt atom is surrounded by two Cl and two P atoms in a square planar arrangement.  相似文献   

10.
The reaction of TiCl4 with Li2[(SiMe2)2(η5-C5H3)2] in toluene at room temperature afforded a mixture of cis- and trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] in a molar ratio of 1/2 after recrystallization. The complex trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] was hydrolyzed immediately by the addition of water to THF solutions to give trans-[(TiCl2)2(μ-O){(SiMe2)2(η5-C5H3)2}] as a solid insoluble in all organic solvents, whereas hydrolysis of cis-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] under different conditions led to the dinuclear μ-oxo complex cis-[(TiCl2)2)(μ-O){(SiMe2)2(η5-C5H3)2}] and two oxo complexes of the same stoichiometry [(TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 as crystalline solids. Alkylation of cis- and trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] with MgCIMe led respectively to the partially alkylated cis-[(TiMe2Cl)2{(SiMe2)2(η5-C5H3)2}] and the totally alkylated trans-[(TiMe3)2{(SiMe2)2(η5-C5H3)2}] compounds. The crystal and molecular structure of the tetranuclear oxo complex [(TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 was determined by X-ray diffraction.  相似文献   

11.
The reaction of RuCl3(H2O), with C5Me4CF3J in refluxing EtOH gives [Ru2(η5-C5Me1CF2)2 (μ-Cl2] (20 in 44% yield. Dimer 2 antiferromagnetic (−2J=200 cm1). The crystal structures of 2 (rhombohedral system, R3 space group, Z=9, R=0.0589) and [Rh2(η5-C5Me4CF3(2Cl2(μ-Cl)2] (3) (rhombohedral system. space group, Z = 9, R = 0.0641) were solved; both complexes have dimeric structures with a trans arrangement of the η5-C5Me4CF4 rings. Comparison of the geometry of 2 and 3 with those of the corresponding η5-C5Me5 complexes shows that lowering the ring symmetry causes significant distortion of the M2(μ-Cl)2 moiety. The analysis of the MCl3 fragment conformations in 2 and 3 and in the η5-C5ME5 analogues shows that they are correlated with the M---M distances. The Cl atoms are displaced by Br on reaction of 2 with KBr in MeOH to give the diamagnetic dimer [Ru2(η5-C5Me4CF3)2Br2 (μ-Br2] (4). Complex 2 reacts with O2 in CH2Cl2 solution at ambient temperature to form a mixture of isomeric η6-fulvene dimers [Ru2(η6-C5Me3CF3 = CH2)2Cl2(μ-Cl)2] (5). Reactions of 5 with CO and allyl chloride give Ru(η5-C5Me3CF3CH2Cl)(CO)2Cl (6) and Ru(η5-C5Me3CF3CF3CH2Cl)(η3-C3H5)Cl2 (7) respectively.  相似文献   

12.
Reactions of [Rh(COD)Cl]2 with the ligand RN(PX2)2 (1: R = C6H5; X = OC6H5) give mono- or disubstituted complexes of the type [Rh2(COD)Cl2{ν2−C6H5N(P(OC6H5)2)2}] or [RhCl{ν2−C6H5 N(P(OC6H5)2)2 }]2 depending on the reaction conditions. Reaction of 1 with [Rh(CO)2Cl]2 gives the symmetric binuclear complex, [Rh(CO)Cl{μ−C6H5N(P(OC6H5)2)2} 2, whereas the same reaction with 2 (R = CH3; X = OC6H5) leads to the formation of an asymmetric complex of the type [Rh(CO)(μ−CO)Cl{μ−CH3N(P(OC6H5)2)2}2 containing both terminal and bridging CO groups. Interestingly the reaction of 3 (R = C6H5, X = OC6H4Br−p with either [Rh(COD)Cl]2 or [Rh(CO)2Cl]2 leads only to the formation of the chlorine bridged binuclear complex, [RhCl{ν2−C6H5N(P(OC6H4Br−p)2)2}]2. The structural elucidation of the complexes was carried out by elemental analyses, IR and 31P NMR spectroscopic data.  相似文献   

13.
The phosphinoalkenes Ph2P(CH2)nCH=CH2 (n= 1, 2, 3) and phosphinoalkynes Ph2P(CH2)n C≡CR (R = H, N = 2, 3; R = CH3, N = 1) have been prepared and reacted with the dirhodium complex (η−C5H5)2Rh2(μ−CO) (μ−η2−CF3C2CF3). Six new complexes of the type (ν−C5H5)2(Rh2(CO) (μ−η1:η1−CF3C2CF3)L, where L is a P-coordinated phosphinoalkene, or phosphinoalkyne have been isolated and fully characterized; the carbonyl and phosphine ligands are predominantly trans on the Rh---Rh bond, but there is spectroscopic evidence that a small amount of the cis-isomer is formed also. Treatment of the dirhodium-phosphinoalkene complexes with (η−CH3C5H4)Mn(CO)2thf resulted in coordination of the manganese to the alkene function. The Rh2---Mn complex [(η−C5H5)2Rh2(CO) (μ−η1:η1−CF3C2CF3) {Ph2P(CH2)3CH=CH2} (η−CH3C5H4)Mn(CO)2] was fully characterized. Simi treatment of the dirhodium-phosphinoalkyne complexes with Co2(CO)8 resulted in the coordination of Co2(CO)6 to the alkyne function. The Rh2---Co2 complex [(η−C5H5)2Rh2(CO) (μ−η1:η1−CF3C2CF3) {Ph2PCH2C≡CCH3}Co2(CO)2], C37H25Co2F6O7PRh2, was fully characteriz spectroscopically, and the molecular structure of this complex was determined by a single crystal X-ray diffraction study. It is triclinic, space group (Ci1, No. 2) with a = 18.454(6), B = 11.418(3), C = 10.124(3) Å, = 112.16(2), β = 102.34(3), γ = 91.62(3)°, Z = 2. Conventional R on |F| was 0.052 fo observed (I > 3σ(I)) reflections. The Rh2 and Co2 parts of the molecule are distinct, the carbonyl and phosphine are mutually trans on the Rh---Rh bond, and the orientations of the alkynes are parallel for Rh2 and perpendicular for Co2. Attempts to induce Rh2Co2 cluster formation were unsuccessful.  相似文献   

14.
It is shown that the reaction of RhCl3·3H2O with acetonitrile normally produces mixtures of mer- and fac-[RhCl3(CH3CN)3] (1a and 1b, respectively). The IR and 1H NMR spectra of these isomers were re-investigated. Their two-dimensional (103Rh,1H) NMR spectra were also recorded. Equilibrium and exchange studies of 1a and 1b in CD3C were performed. It was found that in 1a the exchange rate of the nitrile molecule trans to Cl is much faster than those of mutually trans nitriles. Also the nitrile molecules in 1b underwent fast exchange in CD3CN; however, their rate was slightly faster than that of the more labile CH3CN in 1a. The X-ray crystal structure of mer-[RhCl3(CH3CN)3]·CH3CN (1c) was determined. Crystal data: triclinic space group

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15.
The kinetics of the displacement reactions of the bromide ligands of trans-[FeBr2(depe)2] (depe = Et2PCH2CH2PEt2) by the organonitrile NCCH2C6H4OMe-4, in tetrahydrofuran (either in the absence or in the presence of added Br−), to give the corresponding mono- and dinitrile complexes trans-[FeBr(NCCH2C6H4OMe-4)(depe)2]+ and trans-[Fe(NCCH2C6H4OMe-4)2(depe)2]2+, have been investigated by stopped-flow spectrophotometry. The substitution reaction occurs by a mechanism involving rate-limiting dissociation of bromo ligands to form the unsaturated intermediates [FeBr(depe)2]+ (k1 = 1.52 ± 0.02 s−1) and [Fe(NCR)(depe)2]2+ (k3 = 0.063 ± 0.008 s−1) which add the nitrile ligand to form those nitrile complexes. The competition between the nitrile and Br− for such metal centres has also been investigated and a stronger inhibiting effect of added Br− is observed for the substitution of the second bromo ligand relative to the first one. The kinetic data are rationalized in terms of π-electronic effects of these unsaturated metal centres and of the bromide and nitrile ligands.  相似文献   

16.
Kinetic results are reported for intramolecular PPh3 substitution reactions of Mo(CO)2(η1-L)(PPh3)2(SO2) to form Mo(CO)2(η2-L)(PPh3)(SO2) (L = DMPE = (Me)2PC2H4P(Me)2 and dppe=Ph2PC2H4PPh2) in THF solvent, and for intermolecular SO2 substitutions in Mo(CO)3(η2-L)(η2-SO2) (L = 2,2′-bipyridine, dppe) with phosphorus ligands in CH2Cl2 solvent. Activation parameters for intramolecular PPh3 substitution reactions: ΔH≠ values are 12.3 kcal/mol for dmpe and 16.7 kcal/mol for dppe; ΔS≠ values are −30.3 cal/mol K for dmpe and −16.4 cal/mol K for dppe. These results are consistent with an intramolecular associative mechanism. Substitutions of SO2 in MO(CO)3(η2-L)(η2-SO2) complexes proceed by both dissociative and associative mechanisms. The facile associative pathways for the reactions are discussed in terms of the ability of SO2 to accept a pair of electrons from the metal, with its bonding transformations of η2-SO2 to η1-pyramidal SO2, maintaining a stable 18-e count for the complex in its reaction transition state. The structure of Mo(CO)2(dmpe)(PPh3)(SO2) was determined crystallographically: P21/c, A=9.311(1), B = 16.344(2), C = 18.830(2) Å, ß=91.04(1)°, V=2865.1(7) Å3, Z=4, R(F)=3.49%.  相似文献   

17.
The syntheses and structures of [Ni(H2O)6]2+[MF6]2− (M = Ti,Zr,Hf) and Ni3(py)12F6·7H2O are reported. The former three compounds are isostructural, crystallizing in the trigonal space group (No. 148) with Z = 3. The lattice parameters are a = 9.489(4), C = 9.764(7) Å, with V = 761(1) Å3 for Ti; a = 9.727(2), C = 10.051(3) Å, with V = 823.6(6) Å3 for Zr; and a = 9.724(3), C = 10.028(4)Å, with V = 821.2(8)Å3 for Hf. The structures consist of discrete [Ni(H2O)6]2+ and [MF6]2− octahedra joined by O---HF hydrogen bond Large single crystals were grown in an aqueous hydrofluoric acid solution. Ni3(py)12F6·7H2O crystallizes in the monoclinic space group I2/a (No. 15) with Z = 4. The lattice parameters are a = 16.117(4), B = 8.529(3), C = 46.220(7) Å, β = 92.46(2)°, and V = 6348(5) Å3. The structure consists of discrete Ni(py)4F2 octahedra linked through H---O---HF and H---O---HO hydrogen bonding interactions. Single c were grown from a (HF)x·pyridine/pyridine/water solution.  相似文献   

18.
In a synthetic route that varies from the standard procedure requiring irradiation, the (η6-C6H5Cl)Cr(CO)2PPh3 complex is obtained upon reacting (η6-C6H5Cl)Cr(CO)3 with tetrakis(triphenylphosphine)palladium(0), CuI, and trimethylsilylphenylacetylene in triethylamine. The X-ray crystal structure of the yellow–orange crystals of (η6-C6H5Cl)Cr(CO)2PPh3 allows structural comparisons to related (arene)Cr(CO)2PR3 complexes.  相似文献   

19.
The interaction of 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and its N-methylated derivative 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci) with the incomplete [Mo3S4]4+ cube and the heterometallic [Mo3S4Cu]4+ cube have been investigated by X-ray analysis. The crystal structures of [Mo3S4(taci+ rmC3H6O-H2O)3-4H]·2OH2O (1a, rhombohedral, space group R32, A = 15.964(3), C = 40.59(1) Å, Z = 6), [Mo3S4(tdci)3]Br4·9.5EtOH·5H2O (2a, triclinic, space group

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and [CuBrMo3S4(tdci)3]Br3·11 H2O·EtOH (3a, monoclinic, space group P2,/n, A = 14.887(3), B = 22.570(4), C = 21.974(5) Å, β = 98.54(2)°, Z = 4) revealed andN-N-O and an N-O-O coordination mode for taci and tdci, respectively. In 1a, taci is coordinated as an anion with deprotonated oxygen and nitrogen donors. In addition, the non-coordinating amino group reacted with one equivalent; of acetone, forming a Schiff base condensation product. For 2a, short Mo---O bonds and high pKa values (compared to the aqua ion [Mo3S4(H2O)9]4+) indicate the formation of a zwitterionic form of the tdci ligand with coordinated alkoxo groups and peripheral dimethylammonium groups. No significant differences were found for the structural properties of the Mo-tdci fragment in 2a and 3a. The coordination modes of taci and tdci, as observed in the solid state, are in agreement with the previously reported solution structures, established by NMR spectroscopy. They are attributed to the specific steric requirements of the two ligands and to a pronounced preference of the [Mo3(μS)3(μ3S)]4+ core to coordinate a nitrogen donor trans to μ3S.  相似文献   

20.
HRu2Fe2PdC(CO)12 (η3-ß-C10H15) cluster was prepared in the reaction of (Et4N) [HFe2Ru2C(CO)12] with [Pd(η3-ß-C10H15)Cl]2. X-ray structural study of HRu2Fe2PdC(CO)12 (η3-ß-C10H15) (where ß-C10H15 is ß-pinenyl) revealed a wing-tip butterfly geometry of the metal core and (1R, 2S, 3S, 5R) absolute configuration for both crystallography independent molecules in the crystal. Chiroptical properties of this cluster are compared with other clusters containing a Pd(η3-ß-C10H15) fragment and discussed.  相似文献   

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