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1.
Four complexes of the type [Cu 4I 4(CH 3CN) 2(L) 2], L = aniline derivative: Cu 4I 4(CH 3CN) 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) Å 3; Cu 4I 4(CH 3CN) 2( o-ethylaniline) 2 (II), triclinic, , V = 1734.0(8) Å 3; Cu 4I 4(CH 3CN) 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) Å 3; Cu 4I 4(CH 3CN) 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) Å 3; 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
2.
Reactions of Cr(CO) 3(η 6-BT), in which the Cr is π-coordinated to the benzene ring of benzo[ b]thiophene (BT), with Cp′(CO) 2Re(THF), where Cp′ = η 5-C 5H 5 or η 5-C 5Me 5, give the products Cp′(CO) 2Re(η 2:η 6-μ 2-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(η 2:η 6-μ 2-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-η 2) or the sulfur (η 1(S)). Thus, the electron-withdrawing Cr(CO) 3 group in 3 stabilizes the 2,3-η 2 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 . 相似文献
3.
Kinetic studies of the addition of a wide range of tertiary phosphines and phosphites to the tropylium ring of the cation [Cr(CO) 3(η 7-C 7H 7] + (1) reveal the two-term raw, kobs = k1[PR 3] + k−1. This is consistent with the reversible equilibrium process (i) which is also confirmed from IR and 1H NMR studies. In the case of the highly basic nucleophiles PBu 3n and PEt 2Ph, the rate is dominated by the k1 term and the equilibrium lies far to the right. The first-order rate constants k1, for addition to the tropylium ring decrease markedly down the series PBu 3n>PEt 2Ph>P(4-MeOC 6H 4) 3>P(4-MeC 6H 4) 3>P(C 6H 11 3>PPh 2(4-MeC 6H 4)>PPh 3>P(2-CNC 2H 4) 3>P(OBu n) 3 (overall variation 10 4). This reactivity order parallels the decreasing electron availability at the phosphorus centres, as confirmed by the linear correlation between log k1 and the Tolman Σ χ values for the nucleophiles. Excellent Hammett and Brønsted correlations are also observed for ring addition by a range of P(4-XC 6H 4) 3 nucleophiles. The Brønsted slope, , of 0.7 conirms the major importance of basicity in determining nucleophilicity towards cation 1. Kinetic studies of the related additions of PBu 3n to the cations [M(CO) 3(η 7-C 7H 7] + (M = Mo, W) reveal the rate law, Rate = k1[M][PBu 3n, and show only a small dependence of k1 on the nature of metal (Cr>WMo; 2:1.1:1). These data, together with the associated activation parameters, support a mechanism involving direct addition ( k1) of the phosphorus nucleophiles to the tropylium ring, and are inconsistent with initial rate-determining attack at the metal centre. 相似文献
4.
Isocyanide-substituted Re alkyl complexes cis- p-XC 6H 4CH 2Re(CO) 4(CN- p-tolyl) (X = Cl, OMe) were prepared from the PdO-catalyzed reaction of p-XC 6H 4CH 2Re(CO) 5 (X = Cl, OMe) with p-tolyl isocyanide. On heating in toluene these complexes undergo isocyanide insertion into the Re---C bond to afford iminoacyl complexes which further react to orthometallate the p-tolyl ring. An X-ray crystal structure determination on (CO) 4 (3a) revealed that C 19H 13ClO 4NRe crystallizes in the monoclinic space group P2 1/ c with 4 formulas per unit cell. Unit cell parameters are a = 9.799 (1), B = 15.252 (2), C = 13.569 (2) Å and β = 110.788 (8)°. The structure shows Re---C bond distances indicative of substantial carbenoid character. 相似文献
5.
[Pt(COD)Cl 2] (1) reacts with PPh 2(C 6H 4COOH) (2a,b,c), PPh 2(C 6H 4COONa) (2d), PPh(C 6H 4COOH) 2 (4b,c) and P(C 6H 4COOH) 3 (6b,c) with formation of the corresponding complexes [Pt(L) 2Cl 2] (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)}{PPh 2(C 6H 4COOH-2)}Cl] (bd8) and [ovbar|{PPh 2(C 6H 4COO-2)} 2] (bd9). Reaction of 1 with CO and 2a or 2b gives [Pt(CO)(L)Cl 2] (10a,b), wherea 1 and 2,3-bis(diphenylphosphino) maleic anhydride yields (bd12) and [Pt{Ph 2PC(COOH)=C(COOMe)-PPh 2}Cl 2] (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 P2 1/ 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
6.
The iron(II) compound of formula [Fe(bpym)(NCS) 2] n (bpym = 2,2′-bipyrimidine) has been synthesized and its crystal structure determined by X-ray diffraction methods. It crystallizes in the tetragonal P4 1 (No. 76) and P4 3 space groups, a = 8.849(2), C=16.486(3) Å, V=1290.9(5) Å 3, Z=4, Dc=1.699 g cm −3, Mr=330.2, F(000)=664, λ(Mo K)=0.71073 Å, μ(Mo K)=14.8 cm −1 and T=295 K. A total of 2449 reflections was collected over the range 3≤2≤55°; of these, 1657 were unique and 1321 were considered as observed (13σ( I)) and used in the structural analysis. The final R and Rw residuals were 0.027 and 0.026, respectively. The structure is made up of chiral (Δ and Λ enantiomers crystallize in the same crop) chains of iron(II) atoms bridged by bis-chelating bpym, the electroneutrality being achieved by N-bonded thiocyanato groups in cis position. Each metal atom is in a distorted FeN 6 octahedral environment, the Fe---N bonds ranging from 2.265(3) to 2.028(4)
. The intrachain metal-metal separation is 5.960(1) Å. Variable-temperature magnetic susceptibility data in the temperatyre range 290–4.2 K show that the iron(II) is high-spin and interacts in an antiferromagnetic fashion, the relevant parameters being . The magnitude of the exchange coupling compares well with that reported for other structurally characterized bpym-bridged iron(II) complexes. 相似文献
7.
The reaction of the neutral Tc(V) phenylimido complex [TcCl 3(NPh)(PPh 3) 2] with excess PMe 2Ph in refluxing MeOH gives the cationic, tris-dimethylphenylphosphine complex [TcCl 2(NPh)(PMe 2Ph) 3] +, which is isolated as the tetraphenylborate salt. The IR spectrum of the crystalline product shows a medium intensity band at 1102 cm −1 which is assigned to ν(TcN) from the phenylimido core. The 1H NMR spectrum of the diamagnetic complex shows a series of multiplets in the aryl region and three distinct signals near 2 ppm from the phosphine methyl groups. The X-ray crystal structure, which is the first for a cationic technetium organoimido complex, shows a meridional arrangement of phosphine ligands with a chloride ligand coordinated trans to the phenylimido unit. The TcN bond length of 1.711(2) Å is consistent with the dianionic nature of the organonitrogen core. The Tc---N---C bond angle of 178.8(2)° reflects the sp hybridization of the phenylimido nitrogen atom. The coordination geometry is best described as a distorted octahedron. Crystal data for C 54H 58BCl 2NP 3Tc: triclinic space group . Structure solution based on 9986 observed reflections converged at R = 3.65%, Rw = 5.43%, GOF = 1.82. 相似文献
8.
Rh(I) and Ir(I) complexes of the type [Rh(cod)(η 2-TMPP)] 1+ (1) and M(cod)(η 2-TMPP- O) (M = Rh (2), Ir (3); cod = cyclooctadiene; TMPP = tris(2,4,6-trimethoxyphenyl)phosphine; TMPP- O = mono-demethylated form of TMPP) have been isolated from reactions of [M(cod)Cl] 2 with M′BF 4 (M′ = Ag +, K +, Na +) followed by addition of the tertiary phosphine ligand. This chemistry is dependent on the identity of the metal, as both the cationic phosphine complex and the neutral phosphino-phenoxide compound are stable for Rh(I), whereas only the latter is stable for Ir(I). The three complexes have been characterized by IR and NMR ( 1H and 31P) spectroscopies as well as by cyclic voltammetry. The 1H NMR spectrum of [Rh(cod)(η 2-TMPP)] 1+ (1) is in accord with the formula and reveals that the TMPP phenyl rings are undergoing rapid exchange between coordinated and non-coordinated modes; the corresponding spectra of 2 and 3 support free rotation about the P---C bonds of the unbound phenyl rings with no fluxionality of the bound demethylated ring. The 31P{ 1H} NMR spectrum of the neutral species 2 exhibits a significant upfield shift with respect to the analogous cationic compound 1. This shielding is the result of improved electron donation to the metal from a phenoxide group as compared to an ether substituent. In situ addition of CO to the reaction between TMPP and [Rh(cod)Cl] 2 or [Ir(cod)Cl] 2 in the presence of M′BF 4 results in the isolation of the monocarbonyl species [Rh(TMPP)(η 2-TMPP)(CO)][BF 4] (5) and the stable dicarbonyl compound [Ir(TMPP) 2(CO) 2][BF 4] (4), respectively. Single crystal X-ray data for . The geometry of 4 is square planar, with essentially ideal angles for the mutually trans disposed phosphine and carbonyl ligands, as found in earlier studies for the analogous Rh dicarbonyl compound. The 1H NMR spectrum of 4 supports the assignment of magnetically equivalent phosphorus nuclei in solution. The results of this study indicate that cyclooctadiene is a particularly strong ligand for monovalent late transition metals ligated by TMPP, to the extent that it is inert with respect to substitution in the absence of π-acceptor ligands such as carbon monoxide. 相似文献
9.
The Tc(I) mixed-ligand complex, trans-[Tc(dppe) 2(bu tNC) 2](PF 6) (dppe=bis(diphenylphosphino)ethane, bu tNC=tert-butyl-isocyanide) has been prepared from [Tc(tu−S) 63+ (tu-S=thiourea) and a mixture of both ligands. The compound crystallizes triclinic in the space group ). The technetium atom has a slightly distorted octahedral coordination sphere with the isocyanide ligands in trans-position to each other. By cyclic voltammetry, at a Pt electrode, trans-[Tc(dppe) 2(bu tNC) 2](PF 6) undergoes a single electron reversible oxidation at E1/2ox=0.91 V versus SCE. 相似文献
10.
Treatment of a THF solution of trans-[ReCl(N 2)L 4] (L = PMePh 2) with a cyanamide, NCNR 2 (R = Me, Et or H) or with cyanoguanidine, NCNC(NH 2) 2 , yields mer-[ReCl(N 2)(NCNR 2)L 3] (1) or mer-[Re(N 2)[Re(N 2){NCNC(NH 2) 2} 2L 3]Cl (2), respectively, which, to our knowledge, are the first mixed dinitrogen-cyanamide-type complexes to be reported. The former products (1, R=Me or Et) can also be obtained from reaction of the benzoyldiazenido complex [ReCl 2(NNCOPh)L 3] with NCNR 2 in refluxing methanol; the Re(II) complex mer-[ReCl 2(NCNEt 2)L 3] (3) is also formed (conceivably via an unusual homolysis of the C---N bond of the benzoyldiazenido ligand) and its crystal structure is reported. It shows an unusual pyramidal conformation at the amine N atom of the diethylcyanamide ligand which also exhibits a significant structural trans influence on the phosphine, behaving as a stronger net electron donor than the latter ligand. 相似文献
11.
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 [Mo 3S 4] 4+ cube and the heterometallic [Mo 3S 4Cu] 4+ cube have been investigated by X-ray analysis. The crystal structures of [Mo 3S 4(taci+ rmC 3H 6O-H 2O) 3-4H]·2OH 2O (1a, rhombohedral, space group R32, A = 15.964(3), C = 40.59(1) Å, Z = 6), [Mo 3S 4(tdci) 3]Br 4·9.5EtOH·5H 2O (2a, triclinic, space group and [CuBrMo 3S 4(tdci) 3]Br 3·11 H 2O·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 p Ka values (compared to the aqua ion [Mo 3S 4(H 2O) 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 [Mo 3(μS) 3(μ 3S)] 4+ core to coordinate a nitrogen donor trans to μ 3S. 相似文献
12.
Compounds of formula [Al(CH 3CN) 6][MCl 6] 3(CH 3CN) 3 (M=Ta (1); Nb (2); Sb (3)) have been synthesized from the reactions of MCl 5 and AlCl 3 in acetonitrile and characterized by X-ray crystallography. Complex 1 crystallizes in the tetragonal space group P4/ mbm with a = B = 10.408(2), C = 7.670(3) Å, V = 830.9(4) Å 3 and Z = 2/3. Complex 2 crystallizes in the tetragonal space group P4/mnc with a = B = 330( a), C = 15.320(3) Å 3 V = 1634.8(4) Å 3 and Z = 4/3. Complex 3 also crystallizes in the tetragonal space group P4/ mnc with a = B = 10.313(1), C = 15.238(2) Å, V = 1621.0(1) Å 3 and Z = 4/3. The non-integer Z values for complexes 1–3 result unusual problems of disorder and/or twinning in these crystal structures due to their high symmetry. The M---Cl distances range from 2.329(3) Å in the Ta complex to 2.355(1) Å in the Sb complex, while the Al---N distances are similar in all three complexes, ranging from 1.92(1) to 1.97(1) Å, respectively. Complexes 1–3 are the first structurally characterized complexes that contain a (hexaacetonitrile)aluminum(III) cation. 相似文献
13.
The coordination chemistry of the new bidentate nitrogen ligands 8-(2-pyridyl)quinoline (8-PQ) and 8-(6-methyl-2-pyridyl)quinoline (Me-8-PQ) towards palladium and platinum has been studied. Several (NN)Pd(R)Cl and (NN)Pd(alkene) complexes have been synthesized. The complex (8-PQ)Pd(Me)Cl has been characterised by a single crystal X-ray determination (crystal data triclinic space group ). A fast CO insertion occurs into the palladium-carbon bond of the complexes (NN)Pd(Me)Cl providing the (NN)Pd(C(O)Me)Cl complexes. For (8-PQ)Pd(C(O)Me)Cl an X-ray structure determination has been carried out (crystal data: monoclinic space group P2 1/ c with a=9.084(4), B=10.179(3), C=16.400(3) Å, β=95.59(2)°, V=1509.2(9) Å 3, R=0.043, Z=4). Unexpected in both molecular structures is the large dihedral angle between the plane of the bidentate nitrogen ligand and the coordination plane of the palladium. Both bidentate coordinating ligands 8-PQ and Me-8-PQ show a relatively large bite angle. A monodentate coordination mode has been observed for the complexes (NN)M(PEt 3)Cl 2 (M=Pd, Pt), as the pyridyl group of the ligand is coordinated to the metal while the quinoline group is dissociated from the metal, which is shown in the X-ray structure determination for the complex (8-PQ)Pd(PEt 3)Cl 2 (crystal data: monoclinic space group P2 1/ a with A=15.736(2), B=7.782(1), C=18.255(3) Å, β=102.98(1)°, V=2178.3(6) Å 3, R=0.062, Z=4). 相似文献
14.
The syntheses of nitrosyl–dimethylsulfoxide–ruthenium(II) complexes with general formula mer-[RuCl 3(L)(DMSO)(NO)] (L=DMSO or CD 3CN) is reported. The mer-[RuCl 3(DMSO) 2(NO)] (1) complex was obtained from the reaction of [RuCl 3(NO)] with the sulfoxide ligand in acetone. The mer-[RuCl 3(CD 3CN)(DMSO)(NO)] (2) compound was obtained from mer-[RuCl 3(DMSO) 2(NO)] maintained in deuterated acetonitrile. These data suggest a slow kinetic reaction due the low lability of the DMSO ligand coordinated to the {Ru II–NO +} species. The crystal and molecular structures of (1) and (2) have been determined from X-ray studies. Crystal data: for (1), monoclinic, P21/c, a=8.8340(2) Å, b=12.0230(3) Å, c=13.7064(4) Å, β=114.546(2)°, Z=4, R1=0.0429; for (2), monoclinic, P21/n, a=10.0180(7) Å, b=9.5070(7) Å, c=13.3340(9) Å, β=102.264(4)°, Z=4, R1=0.0472. The spectroscopic characterization of (1), in solid state (infrared spectrum) and in solution (nuclear magnetic resonance and cyclic voltammetry) is also described. 相似文献
15.
The chloro complexes trans-[Pt(Me)(Cl)(PPh 3) 2], after treatment with AgBF 4, react with 1-alkynes HC---C---R in the presence of NEt 3 to afford the corresponding acetylide derivatives trans-[Pt(Me) (C---C---R) (PPh 3) 2] (R = p-tolyl (1), Ph (2), C(CH 3) 3 (3)). These complexes, with the exception of the t-butylacetylide complex, react with the chloroalcohols HO(CH 2) nCl ( n = 2, 3) in the presence of 1 equiv. of HBF 4 to afford the alkyl(chloroalkoxy)carbene complexes trans-[Pt(Me) {C[O(CH 2) nCl](CH 2R) } (PPh 3) 2][BF 4] (R = p-tolyl, N = 2 (4), N = 3 (5); R=Ph, N = 2 (6)). A similar reaction of the bis(acetylide) complex trans-[Pt(C---C---Ph) 2(PMe 2Ph) 2] with 2 equiv. HBF 4 and 3-chloro-1-propanol affords trans-[Pt(C---CPh) {C(OCH 2CH 2CH 2Cl)(CH 2Ph) } (PMe 2Ph) 2][BF 4] (7). T alkyl(chloroalkoxy)-carbene complex trans-[Pt(Me) {C(OCH 2CH 2Cl)(CH 2Ph) } (PPh 3) 2][BF 4] (8) is formed by reaction of trans-[Pt(Me)(Cl)(PPh 3) 2], after treatment with AgBF 4 in HOCH 2CH 2Cl, with phenylacetylene in the presence of 1 equiv. of n-BuLi. The reaction of the dimer [Pt(Cl)(μ-Cl)(PMe 2Ph)] 2 with p-tolylacetylene and 3-chloro-1-propanol yields cis-[PtCl 2{C(OCH 2CH 2CH 2Cl)(CH 2C 6H 4- p-Me}(PMe 2Ph)] (9). The X-ray molecular structure of (8) has been determined. It crystallizes in the orthorhombic system, space group Pna2 1, with a = 11.785(2), B = 29.418(4), C = 15.409(3) Å, V = 4889(1) Å 3 and Z = 4. The carbene ligand is perpendicular to the Pt(II) coordination plane; the PtC(carbene) bond distance is 2.01(1) Å and the short C(carbene)-O bond distance of 1.30(1) Å suggests extensive electronic delocalization within the Pt---C(carbene)---O moietry. 相似文献
16.
The reactions of [(H 5C 6) 3P] 2ReH 6− with (CH 3CN) 3Cr(CO) 3, (diglyme)Mo(CO) 3 or (C 3H 7CN) 3W(CO) 3 led to the formation of [(H 5C 6) 3P] 2ReH 6M(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 P2 1/ n with a = 22.323(6), B = 9.523(2), C = 27.502(5) Å, β = 104.98(2) 0 and V = 5648 Å 3 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
17.
Reaction of LaCl 3·7H 2O containing small amounts of La(NO 3) 3·7H 2O as an impurity with 12-crown-4 or 18-crown-6 in 3:1 CH 3CN:CH 3OH resulted in the isolation of the mixed anion complexes [LaCl 2(NO 3)(12-crown-4)] 2, [La(NO 3)(OH 2) 4(12-crown-4)]Cl 2·CH 3CN and [LaCl 2(NO 3)(18-crown-6)]. The nine-coordinate dimer, [LaCl 2(NO 3)(12-crown-4)] 2, has all of the anions in the inner coordination sphere and La 3+ has a capped square antiprismatic geometry. It crystallizes in the orthorhombic space group Pbca with (at −150 °C) a = 12.938(6), B = 15.704(3), C = 13.962(2) Å, and Dcalc = 2.08 g cm −3 for Z = 4. The second complex isolated from the same reaction, [La(NO 3)(OH 2) 4(12-crown-4)]Cl 2·CH 3CN, has the bidentate nitrate anion in the inner coordination sphere but the two chloride anions are in a hydrogen bonded outer sphere. This complex is ten-coordinate 4A,6B-expanded dodecahedral and crystallizes in the monoclinic space group P2 1 with (at 20 °C) A = 7.651(2), B = 11.704(7), C = 11.608(4) Å, β = 95.11(2)°, and Dcalc = 1.80 g cm −3 for Z = 2. The 18-crown-6 complex, [LaCl 2(NO 3)(18-crown-6)], has all inner sphere anions and has ten-coordinate 4A,6B-expanded dodecahedral La 3+ centers. It crystallizes in the orthorhombic space group Pbca with (at 20 °C) a = 14.122(7), B = 13.563(5), C = 19.311(9) Å, and Dcalc = 1.89 g cm −3 for Z = 8. 相似文献
18.
The new tripodal phosphine CH 3C{CH 2P( m-CF 3C 6H 4) 2} 3, CF 3PPP, was prepared by reacting CH 3C(CH 2Br) 3 with Li +P( m-CF 3C 6H 4) 2−, the latter being best obtained by adding Li +N iPr 2− to PH( m-CF 3C 6H 4) 2. The rhodium complexes [RhCl(CO)(CF 3PPP)], [Rh(LL)(CF 3PPP)](CF 3SO 3) (LL = 2 CO or NBD), [RhX 3(CF 3PPP)], [RhX(MeCN) 3(CF 3PPP)](CF 3SO 3) 2 (X = H and Cl), [RhCl 2(MeCN)(CF 3PPP)](CF 3SO 3) and [Rh(MeCN) 3(CF 3PPP)](CF 3SO 3) 3 were prepared and characterized. The X-ray crystal structure of [Rh(NBD)(CF 3PPP)](CF 3SO 3) is reported. The lower oxygen sensitivity of the CF 3PPP rhodium(I) complexes, relative to the corresponding species with the parent ligand CH 3C(CH 2PPh 2) 3, is attributed to the higher effective nuclear charge on the metal centers caused by the presence of the six CF 3 substituents on the terdentate phosphine. A similar effect may be responsible for the easier hydrolysis of the CF 3PPP-containing, cationic rhodium(III) complexes relative to the corresponding compounds of the parent ligand. 相似文献
19.
The reaction of TiCl 4 with Li 2[(SiMe 2) 2(η 5-C 5H 3) 2] in toluene at room temperature afforded a mixture of cis- and trans-[(TiCl 3) 2{(SiMe 2) 2(η 5-C 5H 3) 2}] in a molar ratio of 1/2 after recrystallization. The complex trans-[(TiCl 3) 2{(SiMe 2) 2(η 5-C 5H 3) 2}] was hydrolyzed immediately by the addition of water to THF solutions to give trans-[(TiCl 2) 2(μ-O){(SiMe 2) 2(η 5-C 5H 3) 2}] as a solid insoluble in all organic solvents, whereas hydrolysis of cis-[(TiCl 3) 2{(SiMe 2) 2(η 5-C 5H 3) 2}] under different conditions led to the dinuclear μ-oxo complex cis-[(TiCl 2) 2)(μ-O){(SiMe 2) 2(η 5-C 5H 3) 2}] and two oxo complexes of the same stoichiometry [(TiCl) 2(μ-O){(SiMe 2) 2(η 5-C 5H 3) 2}] 2(μ-O) 2 as crystalline solids. Alkylation of cis- and trans-[(TiCl 3) 2{(SiMe 2) 2(η 5-C 5H 3) 2}] with MgCIMe led respectively to the partially alkylated cis-[(TiMe 2Cl) 2{(SiMe 2) 2(η 5-C 5H 3) 2}] and the totally alkylated trans-[(TiMe 3) 2{(SiMe 2) 2(η 5-C 5H 3) 2}] compounds. The crystal and molecular structure of the tetranuclear oxo complex [(TiCl) 2(μ-O){(SiMe 2) 2(η 5-C 5H 3) 2}] 2(μ-O) 2 was determined by X-ray diffraction. 相似文献
20.
A new method has been developed for the preparation of nitroaryl transition metal complexes using copper(II) nitrate in the presence of acetic anhydride (Menke conditions) to directly nitrate an aryl group which is already σ-bound to a transition metal centre. Under these conditions ruthenium(II) aryl complexes of the type:
(where R 1=R 2=H; R 1=H, R 2=CH 3; R 1=CH 3, R 2=H) react to yield three distinct types of nitroaryl-containing products (I–III). The preparation and characterisation of these compounds are described. X-ray crystallographic data for one example of each of the three types of compound, are also reported. The compounds that have been studied crystallographically are Ru(C6H4NO2-4)(η2-O2CCH3)(CO)(PPh3)2 (1a), C45H37NO5P2Ru·(CH2Cl2)0.5, a = 20.254(5), b=19.437(8), c=22.629(3) Å, β=115.390(10)°, monoclinic, space group C2/c, Z=8; Ru(C6H4N[O]O-2)- Cl(CO)(PPh3)2 (4a), C43H34ClNO3P2Ru, a=9.331(3), b=12.443(2), c=16.346(3) Å, =82.81(2), β=85.03(2), γ=74.76(2)°, triclinic, space group P
, Z=2; Ru(C6H2CH3-2,NO2-4,N[O]O-6)Cl(CO)(PPh3)2 (5b), C44H35Cl- N2O5P2Ru·(CH2Cl2)2, a=19.497(3), b=14.502(3), c=19.340(5) Å, β=122.79(1)°, monoclinic, space group Cc, Z=4. 相似文献
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