Treatment of the vanadium(II) tetrahydroborate complex trans-V(η1-BH4)2(dmpe)2 with (trimethylsilyl) methyllithium gives the new vanadium(II) alkyl cis-V(CH2SiMe3)2(dmpe)2, where dmpe is the chelating diphosphine 1,2-bis(dimethylphosphino)ethane. Interestingly, this complex could not be prepared from the chloride starting material VCl2(dmpe)2. The CH2SiMe3 complex has a magnetic moment of 3.8 μB, and has been characterized by 1H NMR and EPR spectroscopy. The cis geometry of the CH2SiMe3 complex is somewhat unexpected, but in fact the structure can be rationalized on steric grounds. The X-ray crystal structure of cis-V(CH2SiMe3)2(dmpe)2 is described along with that of the related vanadium(II) alkyl complex trans-VMe2(dmpe)2. Comparisons of the bond distances and angles for VMe2(dmpe) 2, V---C = 2.310(5) Å, V---P = 2.455(5) Å, and P---V---P = 83.5(2)° with those of V(CH2SiMe3)2(dmpe)2, V---C = 2.253(3) Å, V---P = 2.551(1) Å, and P ---V---P = 79.37(3)° show differences due to the differing trans influences of alkyl and phosphine ligands, and due to steric crowding in latter molecule. The V---P bond distances also suggest that metal-phosphorus π-back bonding is important in these early transition metal systems. Crystal data for VMe2(dmpe)2 at 25°C: space group P21/n, with a = 9.041(1) Å, b = 12.815(2) Å, c = 9.905(2) Å, β = 93.20(1)°, V = 1145.8(5) Å3, Z = 2, RF = 0.106, and RwF =0.127 for 74 variables and 728 data for which I 2.58 σ(I); crystal data for V(CH2SiMe3)2(dmpe)2 at −75°C: space group C2/c, with a = 9.652(4) Å, b = 17.958(5) Å, c = 18.524(4) Å, β = 102.07(3)°, V= 3140(3) Å3, Z = 4, RF = 0.033, and RwF = 0.032 for 231 variables and 1946 data for which I 2.58 σ(I). 相似文献
RuHCl(CO)2(PPh3)2 reacts with ethylene under mild conditions (25 psi, 80°C) to yield a propionyl derivative RuCl(C[O]C2H5)(CO)(PPh3)2 which is believed to be coordinatively unsaturated. Unlike the acetyl analogue, RuCl[C[O]C2H5(CO)-(PPh3)2 does not isomerize to RuCl(C2H5)(CO)2(PPh3)2 in solution. Under one atmosphere of carbon monoxide, RuCl(C[O]C2H5(CO)(PPh3)2 exists in equilibrium with two species believed to be RuCl(C[O]C2H5)(CO)2(PPh3)2 and [Ru(C[O]C2H5)(CO)3(PPh3)2]Cl. RuCl(C[O]C2H5)(CO)(PPh3)2 reacts with CO/ AgClO4 to give mer-[Ru(C[O]C2H5)(CO)3(PPh3)2]ClO4, p-tolylisocyanide (RNC) and NaClO4 to give cis-[Ru(C[O]C2H5)(CO)(CNR)2(PPh3)2ClO4, and hydrochloric acid to yield the hydroxycarbene complex, RuCl2(CO)(C[OH]C2H5)(PPh3)2. 相似文献
Reaction of photogenerated (η5?C5H5)2W2(CO)4 with acetylene at 25°C yields a complex of the formula (η5-C5H5)2W2(CO)4(C2H2). The crystal structure of the complex shows it to have a tetrahedrane-like W2C2 core. The C—C bond distance of the C2H2 unit is 1.33 Å which is close to that of ethylene, considerably longer than the 1.20 Å for acetylenes. The W—W distance is 2.987 Å which is ～0.25 Å shorter than the W—W distance in (η5-C5H5)2W2(CO)6 but longer than that expected for (η5-C5H5)2W2(CO)4. By analogy to the parent (η5-C5H5)2M2(CO)6 species, the near-UV absorption in (η5-C5H5)2M2(CO)4(C2H2) is assigned to a σb → σ* transition. Owing to the shorter M—M bond in the C2H2 adducts, the σb → σ* absorption is at higher energy than in the (η5-C5H5)2M2(CO)6 complexes. 相似文献
The rate of the reaction has been investigated at 40–65°C with [HClO4] varying from 0.04 to 0.6 M (μ = 0.6 M, NaClO4). The observed rate law has the form: -d[Cr(NH3)5(NCO)2+]/dt = kobs[Cr(NH3)5(NCO)2+] where kobs = a[H+]2{1 + b[H+]2} and ?1 at 55.0°C, a = 0.36 M?1 s?2 and b = 6.9 × 10?3 M?1 s?1. The rate of loss of Cr(NH3)5(NCO)2+ increases with increasing acidity to a limiting value (at [H+] ～ 0.5 M) but the yield of Cr(NH3)63+ decreases with increasing [H+] and increases with increasing temperature. In the kinetic studies the maximum yield of Cr(NH3)63+ was 35% but a synthetic procedure has been developed to give a 60% yield. 相似文献
Ph2P(O)C(S)N(H)R (R Me, Ph) reacts with M(CO)3(η5-C5H5)Cl (M Mo, W) in the presence of Et3N to give M(CO)2(η5-C5H5)(Ph2P(O)C(S)NR). The deprotonated ligand coordinates in a bidentate manner through N and S to give a four-membered ring system. M(CO)3(PPh3)2Cl2 (M Mo, W) reacts with Ph2P(O)C(S)N(H)R (R Me, Ph) in the presence of Et3N to give complexes in which the central metal atoms are seven coordinate through two ligands bonded via O and S to form five-membered ring systems, one PPh3, and two CO groups. The complexes were characterised by elemental analyses, IR, 1H NMR, and 31P NMR spectroscopy, and an X-ray structural analysis of Mo(CO)2(PPh3)(Ph2P(O)C(S)NPh)2 · CH2Cl2. 相似文献
The ionic complex [(π-C5H5)2Zr(H2O)3]2+(CF3SO3?)2·THF, which corresponds to the 18-electron rule, is formed in the reaction of (π-C5H5)2Zr(CF3SO3)2(THF) with H2O in tetrahydrofuran. It crystallizes in the hexagonal space group P63 with Z = 6 and unit cell dimensions at ? 100°C of a 21.945(5) and c 8.711(3) Å. The geometry of the (π-C5H5)2Zr moiety (length of the vectors between Zr and the C5 ring centroids: 2.210 and 2.193 Å; angle between these vectors: 129.0°; angle between the C5 ring normals: 128.3°) agrees with that of neutral, four-coordinate (π-C5H5)2ZrX2 compounds. The three H2O ligands lie in the plane that bisects the angle between the C5 ring planes. The ZrO distances are 2.239(7), 2.195(7), and 2.261(7) Å. The CF3SO3? anions and the THF molecule of crystallization are packed around the complex cation in such a way that their oxygen atoms point towards the H2O ligands. The CF3 sides of the anion, on the other hand, are clustered together so as to produce hydrophobic domains in the crystal structure. 相似文献
The reactions of Fe(CO)5, Fe(CO)4P(C6H5)3, M(CO)6 (M W, Mo, Cr), and (CH3C5H4Mn(CO)3 with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K+Fe(CO)4-(CHO) by hydride transfer from KBH(OCH3)3 allowing isolation of [P(C6H5)3]2-Nn+Fe(CO)4(CHO)? in 50% yield. Lower yields were obtained with LiBH(C2H5)3, and other hydride sources gave little or no formyl product. The stability of Fe(CO)4(CHO)? in THP was found to depend on the cation, decreasing in the order [P(C6H5)3]2N+ > K+ > Na+ > Li+. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)4-P(C6H5)3 gave K2Fe(CO)4 when treated with KHB(OCH3)3. When treated with LiBH(C2H5)3, W(CO)6 gave a mixture of HW2(CO)10?and (OC)5W(COC2H5)?; the latter was methylated to give the carbene complex (OC)5WC(OCH3)C2H5. 相似文献
1-Allyl-4-aminopyridinium chloride reacts with Cu(NO3)2 · 3H2O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound
[(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2] (I). The crystals of compound I are monoclinic: space group P21/c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ?3. The direct interaction of 1-allylquinolinium nitrate with Cu(NO3)2 · 3H2O in a methanolic solution in the presence of metallic copper yields crystals of compound [C9H7N(C3H5)Cu(NO3)2] (II). The crystals of compound II are triclinic: space group P
, a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ?3. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2}n. Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium
cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with
two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The
crystal structure of compound II is built-up of the isolated L2Cu2(NO3)4 fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment
of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L2Cu2(NO3)4 fragments are additionally joined by the C-H…O hydrogen bonds.
Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No.
6, pp. 458–462. 相似文献
[Pd(C6F5)2(CNR)2] (R = Cy, But, p-MeC6H4 (p-Tol)) react with [PdCl2(NCPh)2] to give [Pd2(μ-Cl)2(C6F5)2(CNR)2]. In refluxing benzene insertion of isocyanide into the C6F5Pd bonds occurs only for R = p-Tol, to give a imidoyl bridged polynuclear complex cis-[Pd2 (μ-Cl)2[μ-C(C6F5) = N(Tol-p)]2n]. This complex reacts with (a) Tl(acac) to give [Pd2{μ-C(C6F5) = N(Tol-p)}2(acac)2]; (b) neutral monodentate ligands to afford dimeric complexes [Pd2{μ-C(C6F5) = N(Tol-p)}2Cl2L2] (L = NMe3, py, 4-Me-py, SC4H8), and (c) isocyanides to give insoluble complexes of the same composition which are thought to be polymeric, [(CNR)Cl{μ-C(C6F5) = (p-Tol)}]n (R = p-Tol, Me, But). Thermal decomposition of cis-[Pd2 (μ-Cl)2 [μ-C(C6F5) = N( p-Tol)]2n] gives the diazabutadiene species (p-Tol)NC(C6F5)C(C6F5)N(p-Tol) in high yield. 相似文献
A new metal-metal bonded binuclear iron system [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)2]2 (2) has been prepared by treating two equivalents of NaCp with one equivalent of ClSi(Me)2CH2CH2SiClMe2 obtaining the intermediate (C5H5)Si(Me)2CH2CH2Si(Me)2(C5H5) which then is directly allowed to react with Fe(CO)5 given 2 in 30% yield. From this cyclopentadienyldisilyl linked system three new binuclear irom complexes are formed. Treatment of 2 with Na/Hg in THF produced the dianion [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)2?]2 which is quenched with CH3I giving [Me2SiCH2CH2SiMe2][η5-C4H4Fe(CO)2CH3]2 (4) in 76% yield. Complex 2 is oxidized with 1.2 equivalent of I2 to give [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)2I]2 (5) in 85% yield. Photolysis of 5 (1 equiv.) and PPh3 (3 equiv.) results in the formation of the bis-substituted compound [Me2SiCH2CH2SiMe2][η5-C5H4Fe(CO)(PPh3)I]2 (6). These four new binuclear iron complexes are characterized by 1H, 13C, and 31P NMR and IR spectroscopy. 相似文献
o(CO)3 (M = Mo, W; R = Me, Ph, p-MeC6H4) (2) (obtained from (CO)3CpMCH2CCR (1) and Co2(CO)8) to give (CO)3
Cp(CO)2 (3) was further investigated by a crossover experiment. Thus, reaction of an equimolar mixture of 2b (M = W, Cp = η5-C5H5, R = Ph) and 2e (M = W, Cp = η5-C5H4Me; R = p-MeC6H4) with CF3COOH affords only 3b (same M, Cp, and R as 2b) and 3e (same M, Cp, and R as 2e) to show an intramolecular nature of this transformation. Reaction of (CO)3CpWCH2CCPh (1b) with Co4(CO)12 was also examined and found to yield 2b exclusively. Treatment of 1 with Cp2Mo2(CO)4 at 0–5°C provides thermally sensitive compounds, possibly (CO)2Cp
Full-size image (1K)
oCp(CO)2 (5), which decompose at room temperature to give Cp2Mo2(CO)6 as the only isolated product. 相似文献
The complex [NiCl2(PMe3)2] reacts with one equivalent of mg(CH2CMe3)Cl to yield the monoalkyl derivative trans-[Ni(CH2CMe3)Cl(PMe3)2], which can be carbonylated at room temperature and pressure to afford the acyl [Ni(COCH2CMe3)Cl(PMe3)2]. Other related alkyl and acyl complexes of composition [Ni(R)(NCS)(PMe3)2] (R = CH2CMe3, COCH2CMe3) and [Ni(R)(η-C5H5)L] (L = PMe3, R = CH2CMe3, COCH2CMe3; L = PPh3, R = CH2CMe2Ph) have been similarly prepared. Dialkyl derivatives [NiR2(dmpe)] (R = CH2SiMe3, CH2CMe2Ph; dmpe = 1,2-bis(dimethylphosphine)ethane, Me2PCH2 CH2PMe2) have been obtained by phosphine replacement of the labile pyridine and NNN′N′-tetramethylethylenediamine ligands in the corresponding [Ni(CH2SiMe3)2(py)2] and [Ni(CH2CMe2Ph)2(tmen)] complexes. A single-crystal X-ray determination carried out on the previously reported trimethylphosphine derivative [Ni(CH2SiMe3)2(PMe3)2] shows the complex belongs to the orthorhombic space group Pbcn, with a = 14.345(4), b = 12.656(3), c = 12.815(3) Å, Z = 4 and R 0.077 for 535 independent observed reflections. The phosphine ligands occupy mutually trans positions P-Ni-P 146.9(3)° in a distorted square-planar arrangement. 相似文献
Bis(cycloocta-1,5-diene)platinum reacts with 2,3,4,5-tetraphenylfulvene to afford the complex [Pt(η2-CH2C5Ph4)(cod)] (cod C8H12) in which the metal atom is coordinated to the exo-cyclic double bond of the fulvene. Related compounds [Pt(η2-CH2C5Ph4L2] (L PPh3, PMePh2, PMe2Ph, AsPh3 or CNBut have also been prepared and characterised. Reaction of the complexes [Pt(C2H4)2(L)] (L P(cyclo-C6H11)3, PPh3 or AsPh3) with 2,3,4,5-tetraphenylfulvene yields the compounds [Pt(C2H4)(η2-CH2C5PH4)(L)]. NMR data for the new species are reported and discussed. 6,6-Diphenylfulvene reacts with [Pt(cod)2] and PPh3 ( mol ratio) to give the complex [Pt(η2-C5H4CPh2)-(PPh3)2] in which the metal atom is bonded to carbon atoms C(2) and C(3) of the fulvene ring. This was established by an X-ray diffraction study. Crystals are monoclinic, space group P21/n, with Z 4 in a unit cell of dimensions a 13.761(4), b 21.653(13), c 17.395(6) Å, β, 104.46(2)°. The structure has been solved and refined to R 0.064 (R′ 0.064) for 3139 independent diffracted intensifies measured at room temperature. The platinum atom is in a trigonal environment formed by the two ligated phosphorus atoms and the CC bond of the fulvene which is elongated to 1.52(3) Å. The c5 fulvene ring is planar, and makes an angle of 108° with the coordination plane around the platinum. In this plane the metal atom is slightly asymmetrically bonded with PtC 2.15(2) and 2.24(2) Å, and PtP 2.280(6) and 2.301(6) Å. 相似文献
The complex Os3(CO)9(μ2-H)2(μ3-S) reacts with KOH/MeOH to produce the anionic complex [Os3(CO)9(μ2-H)(μ3-S)?, which reacts in turn with RO+ (R = Me, Et) to form HOs3(CO)9SR. This complex is especially reactive towards ligands L (L = C2H4, CO, PR3 and MeCN) to generate complexes of the type Os3(CO)9(μ2-H)(μ2-SR)(L). At 125°C the complex Os3(CO)9(μ2-H)(μ2-SR)(C2H4) (in the presence of C2H4) ejects RH and CO to form Os3(CO)8(μ2-H)?(μ3-S)(CHCH2). The structures of the new complexes are described and the probable reaction pathways discussed. 相似文献
Crystals of the rhenium cluster complex (H3O)4[(C2H5)4N]6[Th2Cl4(H2O)12O]3[Re4Se4(CN)12]4 are obtained in an acidic (HCl) aqueous solution by the reaction of cluster salt K4[Re4Se4(CN)12]·6H2O with ThCl4 and (C2H5)4NCl. Single crystal X-ray analysis shows that the title compound is ionic and crystallizes in the cubic crystal system (a = 22.7322(3) ?, V = 11746.93(27) ?3, Z = 2, I4 3m space group, R = 0.0350). It contains [Th2Cl4(H2O)12O]2+ cations with two thorium atoms bonded to each other through the bridging oxygen atom forming an angle of 180° in the structure. 相似文献
FeIIFeIII2F8(H2O)2 and MnFe2F8(H2O)2, grown by hydrothermal synthesis (), crystallize in the monoclinic system with cell dimensions (Å): a = 7.609(5), b = 7.514(6), c = 7.453(4), β = 118.21(3)°; and a = 7.589(6), b = 7.503(8), c = 7.449(5), β = 118.06(3)°, and space group . The structure is related to that of . It is described in terms of perovskite type layers of Fe3+ octahedra separated by Fe2+ or Mn2+ octahedra, or in terms of shifted hexagonal bronze type layers. Both compounds present a weak ferromagnetism below TN (157 and 156 K, respectively). Mössbauer spectroscopy points to an “idle spin” behavior for FeIIFeIII2F8(H2O)2: only Fe3+ spins order at TN, while the Fe2+ spins remain paramagnetic between 157 and 35 K. Below 35 K, the hyperfine magnetic field at the Fe2+ nuclei is very weak: Hhf = 47 kOe at T = 4.2 K. For MnFe2F8(H2O)2, Mn2+ spin disorder is expected at 4.2 K. This “idle spin” behavior is due to magnetic frustration. 相似文献
The [Ni(DDM)2(NO3)2(H2O)2] complex (DDM is 4,4-diaminodiphenylmethane [CH2(C6H4NH2)2]) is synthesized, and its structure is determined. The crystals are triclinic, space group P
, a = 5.846(1) ?, b = 9.450(2) ?, c = 13.390(3) ?, α = 105.63(3)°, β = 98.13(3)°, γ = 105.84(3)°, V = 666.6(2) ?3, ρcalcd = 1.553 g/cm3, Z = 2. The Ni(II) ion (in the inversion center) is bound to a distorted octahedral array formed by the nitrogen atoms of the
primary amino groups of the DDM molecules and the oxygen atoms of the monodentate nitrato groups and water molecules (Ni(1)-N(3)
2.119(2) ?, Ni(1)-O(1) 2.122(2) ?, Ni(1)-O(w) 2.047(2) ?, angles at the Ni atoms vary in the 85.08(9)°–94.92(9)° interval).
The structure contains supramolecular metallacycles formed by the O(w)-H…N(2) hydrogen bonds between the coordinated H2O molecules and the terminal amino groups of DDM. The metallacycles are joined by the Ni2+ ions into infinite chains running in the [111] direction.
Original Russian Text ? Yu.V. Kokunov, V.V. Kovalev, Yu.E. Gorbunova, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008,
Vol. 53, No. 11, pp. 1838–1843. 相似文献
Syntheses and single-crystal X-ray diffraction studies have been completed on two cycloruthenapentadienyl (CO)6Ru2L2 derivatives, with L = CH2OHC = CCH2OH and C2H5C=CCH2CH2OH respectively. Crystal data are as follows: for [(CO)3RuC4(CH2OH)4]Ru(CO)3·H2O, P21/c, a 13.72(1), b 9.501(4), c 14.86(1) Å, β 101.10(6)°, Rw = 0.052 for 1911 reflections; for [(CO)3RuC4(CH2CH2OH)2(C2H5)2]Ru(CO)3, P21/c, a 9.191(3), b 16.732(4), c 14.903(3) Å, β 113.61(4)°, Rw = 0.042 for 2865 reflections. Both compounds are built up from binuclear units, each unit being regarded as a Ru(CO)3 fragment π-bonded to a cycloruthenapentadienyl ring. The molecular parameters are compared with those of known cyclometallapentadienyl complexes of transition metals. The presence of a semi-bridging CO group is discussed. 相似文献
The complex (η5-C5H5)NiRu3(μ-H)(CO)9(μ4-η2-CCHBut) (1a) reacts with olefins to give several organic products, including species derived from the coupling of the vinylidene ligand with an olefin-derived =CRR′ fragment, representing the first example of a (non catalytic) olefin metathesis reaction involving a metal cluster; other complexes structurally or chemically related to the compound 1a have also been treated with olefins and alkynes. 相似文献
