共查询到20条相似文献,搜索用时 13 毫秒
1.
The compounds (Me4N)[A(M(SC(O)Ph)3)2] (A = K, M = Cd (2); A = Na, M = Hg (3); and A = K, M = Hg (4)) were synthesized by reacting the appropriate metal chloride with A+PhC(O)S- and Me4NCl in the ratios 1:3:1 and 2:6:1. The structures of these compounds were determined by single-crystal X-ray diffraction methods. All the compounds are isomorphous, isostructural, and crystallized in the space group P1 with Z = 1. Single-crystal data for 2: a = 106670(2) A, b = 111522(2) A, c = 119294(2) A, alpha = 71782(1) degrees, beta = 85208(1) degrees, gamma = 69418(1) degrees, V = 126140(4) A3, Dcalc = 1528 g cm-3. Single-crystal data for 3: a = 10840(2) A, b = 10946(4) A, c = 12006(3) A, alpha = 7218(2) degrees, beta = 8675(2) degrees, gamma = 6743(2) degrees, V = 12493(6) A3, Dcalc = 1756 g cm-3. Single-crystal data for 4: a = 104780(1) A, b = 112563(2) A, c = 119827(2) A, alpha = 71574(1) degrees, beta = 85084(1) degrees, gamma = 70705(1) degrees, V = 126523(3) A3, Dcalc = 1755 g cm-3. In the [A(M(SC(O)Ph)3)2]- anions, each M(II) atom is bonded to three thiobenzoate ligands through sulfur atoms, giving a trigonal planar MS3 geometry. The carbonyl oxygen atoms from the two [M(SC(O)Ph)3]- anions are bonded to the alkali metal atom, providing an octahedral environment. Solution metal NMR studies showed the concentration-dependent dissociation of the alkali metal ions in the trinuclear anions. 相似文献
2.
3.
Raebiger JW Manson JL Sommer RD Geiser U Rheingold AL Miller JS 《Inorganic chemistry》2001,40(11):2578-2581
The homoleptic complexes [Ph(4)P](2)[Co[N(CN)(2)](4)] and [Ph(4)P][M[N(CN)(2)](3)] [M = Co, Mn] have been structurally as well as magnetically characterized. The complexes containing [M[N(CN)(2)](4)](2-) form 1-D chains, which are bridged via a common dicyanamide ligand in [M[N(CN)(2)](3)](-) to form a 2-D structure. The five-atom [NCNCN](-) bridging ligands lead to weak magnetic coupling along a chain. The six [NCNCN](-) ligands lead to a (4)T(1g) ground state for Co(II) which has an unquenched spin-orbit coupling that is reflected in the magnetic properties. Long-range magnetic ordering was not observed in any of these materials. 相似文献
4.
New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] and [M4Cl4(PPh2)4(PnPr3)2] (M = Zn, Cd) AgCl reacts with Ph2PSiMe3 in the presence of a tertiary Phosphine PMe3 or PtBu3 to form the multinuclear complexes [Ag4(PPh2)4(PMe3)4] ( 1 ) and [Ag6(PPh2)6(PtBu3)2] ( 2 ). In analogy to that MCl2 reacts with Ph2PSiMe3 in the presence of PnPr3 to form the two multinuclear complexes [M4Cl4(PPh2)4(PnPr3)2] (M = Zn ( 3 ), Cd ( 4 )). The structures were characterized by X-ray single crystal structure analysis ( 1 : space group Pna21 (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2 : space group P–1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3 : space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4 : space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh2)2]n (M = Zn, Cd). 相似文献
5.
6.
Sharutin V. V. Sharutina O. K. Senchurin V. S. 《Russian Journal of General Chemistry》2022,92(7):1309-1316
Russian Journal of General Chemistry - Palladium phosphonium complexes with mononuclear anions [Ph3PCH2CN][PdBr4], [Ph4P][PdBr4], and [Ph3PC5H9-cyclo][PdBr3(Et2SO)] were synthesized by the reaction... 相似文献
7.
8.
The salts (Ph(4)E)[M(SOCPh)(3)] (M = Zn, Cd, or Hg; E = P or As) are produced by the reaction of Zn(NO(3))(2).6 H(2)O, Cd(NO(3))(2).4H(2)O or HgCl(2) with Et(3)NH(+)PhCOS(-) and (Ph(4)E)X (E = P, X = Br; E = As, X = Cl) in aqueous MeOH in the ratios M(II):PhCOS(-):Ph(4)E(+) = 1:>/=3:>/=1. The crystal structures of (Ph(4)P)[Zn(SOCPh)(3)] (1), (Ph(4)As)[Cd(SOCPh)(3)] (2) and (Ph(4)P)[Hg(SOCPh)(3)] (3) have been determined by single-crystal X-ray diffraction experiments. Crystal data for 1: triclinic; space group P&onemacr;; Z = 2; a = 10.819(2) ?, b = 13.219(3) ?, c = 15.951(3) ?; alpha = 101.75(2) degrees, beta = 97.92(1) degrees, gamma = 109.18(2) degrees. Crystal data for 2: triclinic; space group P&onemacr;; Z= 2; a = 10.741(2) ?, b = 13.168(2) ?, c = 15.809(2) ?; alpha = 101.00(1) degrees, beta = 97.65(1) degrees, gamma = 109.88(1) degrees. Crystal data for 3: monoclinic; space group P2(1)/n; Z = 4; a = 13.302(2) ?, b = 14.276(2) ?, c = 21.108(2) ?; beta = 90.92(1) degrees. The compounds 1 and 2 are isomorphous and isostructural. In the anions [M(SOCPh)(3)](-) the metal atoms have trigonal planar coordination by three sulfur atoms. The metal atoms are further more weakly coordinated intramolecularly to one (M = Hg) or two (M = Zn, Cd) thiobenzoate oxygen atom(s). Using the Bond Valence approach it is found that the contribution of M.O bonding to the total bonding is in the order Cd > Zn > Hg. The metal ((113)Cd, (199)Hg) NMR signals of [M(SOCPh)(3)](-) (M = Cd, Hg) are more shielded than those found for MS(3) kernels in thiolate complexes, a difference attributed to the M(.)O bonding in the thiobenzoate complexes. The (113)Cd resonance of [Cd(SOCPh)(3)](-) in dilute solution is in the region anticipated from dilution data for [Na(Cd{SOCPh}(3))(2)](-). 相似文献
9.
S. A. Gromilov S. P. Khranenko P. E. Plyusnin P. Yu. Vanina N. V. Kuratieva 《Journal of Structural Chemistry》2013,54(6):1077-1082
By single crystal X-ray diffraction the crystal structure of a series of [M(NH3)5Cl]WO4 (M = Cr, Rh) complex salts is determined. The features of thermal expansion of the single crystal of [Cr(NH3)5Cl]WO4 are studied by low- and high-temperature X-ray diffractometry in the temperature range from ?173°C to +127°C. It is shown that with an increase in the temperature, W-O distances and ∠O-W-O bond angles equalize and the average W-O distances decrease by 0.012 Å. The thermal properties of the salts in different gaseous atmospheres are examined and the phase composition of the obtained products is studied. 相似文献
10.
Exploiting the ability of the [M(SC[O]Ph)(4)](-) anion to behave like an anionic metalloligand, we have synthesized [Li[Ga(SC[O]Ph)(4)]] (1), [Li[In(SC[O]Ph)(4)]] (2), [Na[Ga(SC[O]Ph)(4)]] (3), [Na(MeCN)[In(SC[O]Ph)(4)]] (4), [K[Ga(SC[O]Ph)(4)]] (5), and [K(MeCN)(2)[In(SC[O]Ph)(4)]] (6) by reacting MX(3) and PhC[O]S(-)A(+) (M = Ga(III) and In(III); X = Cl(-) and NO(3)(-); and A = Li(I), Na(I), and K(I)) in the molar ratio 1:4. The structures of 2, 4, and 6 determined by X-ray crystallography indicate that they have a one-dimensional coordination polymeric structure, and structural variations may be attributed to the change in the alkali metal ion from Li(I) to Na(I) to K(I). Crystal data for 2 x 0.5MeCN x 0.25H(2)O: monoclinic space group C2/c, a = 24.5766(8) A, b = 13.2758(5) A, c = 19.9983(8) A, beta = 108.426(1) degrees, Z = 8, and V = 6190.4(4) A(3). Crystal data for 4: monoclinic space group P2(1)/c, a = 10.5774(7) A, b = 21.9723(15) A, c = 14.4196(10) A, beta = 110.121(1) degrees, Z = 4, and V = 3146.7(4) A(3). Crystal data for 6: monoclinic space group P2(1)/c, a = 12.307(3) A, b = 13.672(3) A, c = 20.575(4) A, beta = 92.356(4) degrees, Z = 4, and V = 3458.8(12) A(3). The thermal decomposition of these compounds indicated the formation of the corresponding AMS(2) materials. 相似文献
11.
12.
(Et3NH)[In(SeC{O}Ph)4].H2O (1) along with heterobimetallic and polymeric metal selenocarboxylates, namely [NaGa(SeC{O}Ph)4] (2), [K(MeCN)2Ga(SeC{O}Ph)4] (3), [NaIn(SeC{O}Ph)4] (4), [K(MeCN)2In(SeC{O}Ph)4] (5), [(Ph3P)2CuIn(SeC{O}Ph)4].CH2Cl2 (6), and [(Ph3P)2AgIn(SeC{O}Ph)4].CH2Cl2 (7), have been synthesized by incorporating either alkali metal ions (Na+ and K+) or group 11 metal ions (Cu(I) and Ag(I)) into the [M(SeC{O}Ph)4]- anion. Crystal structures determined by X-ray crystallography indicate that 3 and 5 have one-dimensional coordination polymeric structures while 6 and 7 have an M(mu-Se)2In (M = Cu, Ag) core. The thermal decomposition of these compounds except 4 lead to the formation of the corresponding metal selenides as confirmed by thermogravimetric analysis and in some cases by powder X-ray diffraction studies. 相似文献
13.
14.
Mitchell K Huang FQ McFarland AD Haynes CL Somers RC Van Duyne RP Ibers JA 《Inorganic chemistry》2003,42(13):4109-4116
CsLnCdSe(3) (Ln = Ce, Pr, Sm, Gd, Tb, Dy, Y) and CsLnHgSe(3) (Ln = La, Ce, Pr, Nd, Sm, Gd, Y) have been synthesized at 1123 K. These isostructural materials crystallize in the layered KZrCuS(3) structure type in the orthorhombic space group Cmcm and are group X extensions of the previously characterized Zn compounds. The structure is composed of two-dimensional [LnMSe(3)] layers that stack perpendicular to [010] and are separated by layers of face- and edge-sharing CsSe(8) bicapped trigonal prisms. Because there are no Se-Se bonds in the structure of CsLnMSe(3) (M = Zn, Cd, Hg), the formal oxidation states of Cs/Ln/M/Se are 1+/3+/2+/2-. CsSmHgSe(3) does not adhere to the Curie-Weiss law, whereas CsCeHgSe(3) and CsGdHgSe(3) are Curie-Weiss paramagnets with micro (eff) values of 2.77 and 7.90 micro (B), corresponding well with the theoretical values of 2.54 and 7.94 micro (B) for Ce(3+) and Gd(3+), respectively. Single-crystal optical absorption measurements were performed with polarized light perpendicular to the (010) and (001) crystal faces of these materials. The band gaps of the (010) crystal faces range from 1.94 eV (CsCeHgSe(3)) to 2.58 eV (CsYCdSe(3)) whereas those of the (001) crystal faces span the range 2.37 eV (CsSmHgSe(3)) to 2.54 eV (CsYCdSe(3) and CsYHgSe(3)). The largest band gap variation between crystal faces is 0.06 eV for CsYCdSe(3). Theoretical calculations for CsYMSe(3) indicate that these materials are direct band gap semiconductors whose colors and optical band gaps are dependent upon the orbitals of Y, M, and Se. 相似文献
15.
The first solid-state NMR investigation of dichalcogenoimidodiphosphinato complexes, M[N(R(2)PE)(2)](n), is presented. The single-source precursors for metal-selenide materials, M[N((i)Pr(2)PSe)(2)](2) (M = Zn, Cd, Hg), were studied by solid-state (31)P, (77)Se, (113)Cd, and (199)Hg NMR at 4.7, 7.0, and 11.7 T, representing the only (77)Se NMR measurements, and in the case of Cd[N((i)Pr(2)PSe)(2)](2)(113)Cd NMR measurements, to have been performed on these complexes. Residual dipolar coupling between (14)N and (31)P was observed in solid-state (31)P NMR spectra at 4.7 and 7.0 T yielding average values of R((31)P,(14)N)(eff) = 880 Hz, C(Q)((14)N) = 3.0 MHz, (1)J((31)P,(14)N)(iso) = 15 Hz, alpha = 90 degrees , beta = 26 degrees . The solid-state NMR spectra obtained were used to determine the respective phosphorus, selenium, cadmium, and mercury chemical shift tensors along with the indirect spin-spin coupling constants: (1)J((77)Se,(31)P)(iso), (1)J((111/113)Cd,(77)Se)(iso), (1)J((199)Hg,(77)Se)(iso), and (2)J((199)Hg,(31)P)(iso). Density functional theory magnetic shielding tensor calculations were performed yielding the orientations of the corresponding chemical shift tensors. For this series of complexes the phosphorus magnetic shielding tensors are essentially identical, the selenium magnetic shielding tensors are also very similar with respect to each other, and the magnetic shielding tensors of the central metals, cadmium and mercury, display near axial symmetry demonstrating an expected deviation from local S(4) symmetry. 相似文献
16.
《Journal of organometallic chemistry》1986,302(1):87-99
Syntheses of [M(P(O)(OMe)2)(P(OMe)3)4] (M = Co, Rh, Ir) and variable temperature 31P NMR studies are described, and mechanistic implications discussed. 相似文献
17.
Reactions of Na[N(TePPri2)2] with the appropriate metal halide produce the air-stable complexes M[N(TePPri2)2-Te,Te']n (n = 2, M = Zn, Cd, Hg; n = 3, M = Sb, Bi), which adopt distorted tetrahedral (M = Zn, Cd, Hg) and octahedral (M = Sb, Bi) structures, respectively. 相似文献
18.
Zincselenide- and Zinctellurideclusters with Phenylselenolate- and Phenyltellurolateligands. The Crystal Structures of [NEt4]2[Zn4Cl4(SePh)6], [NEt4]2[Zn8Cl4Se(SePh)12], [Zn8Se(SePh)14(PnPr3)2], [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr, Ph), and [Zn10Te4(TePh)12(PR3)2] (R = nPr, Ph) In the prescence of NEt4Cl ZnCl2 reacts with PhSeSiMe3 or a mixture of PhSeSiMe3/Se(SiMe3)2 to form the ionic complexes [NEt4]2[Zn4Cl4(SePh)6] 1 or [NEt4]2[Zn8Cl4Se(SePh)12] 2 respectively. The use of PnPr3 instead of the quarternary ammonia salt leads in toluene to the formation of crystalline [Zn8Se(SePh)14(PnPr3)2] 3 . Reactions of ZnCl2 with PhTeSiMe3 and tertiary phosphines result in acetone in crystallisation of the ionic clusters [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr 4 , Ph 5 ) and in THF of the uncharged [Zn10Te4(TePh)12(PR3)2] (R = nPr 6 , Ph 7 ). The structures of 1–7 were obtained by X-ray single crystal structure. ( 1 : space group P21/n (No. 14), Z = 4, a = 1212,4(2) pm, b = 3726,1(8) pm, c = 1379,4(3) pm β = 99,83(3)°; 2 space group P21/c (Nr. 14), Z = 4, a = 3848,6(8) pm, b = 1784,9(4) pm, c = 3432,0(7) pm, β = 97,78(3)°; 3 : space group Pnn2 (No. 34), Z = 2, a = 2027,8(4) pm, b = 2162,3(4) pm, c = 1668,5(3) pm; 4 : space group P21/c (No. 14), Z = 4, a = 1899,8(4) pm, b = 2227,0(5) pm, c = 2939,0(6) pm, β = 101,35(3)°; 5 : space group space group P21/n (No. 14), Z = 4, a = 2231,0(5) pm, b = 1919,9(4) pm, c = 3139,5(6) pm, β = 109,97(4)°; 6 : space group I41/a (No. 88), Z = 4, a = b = 2566,0(4) pm, c = 2130,1(4) pm; 7 : space group P1¯ (No. 2), Z = 2, a = 2068,4(4) pm, b = 2187,8(4) pm, c = 2351,5(5) pm, α = 70,36°, β = 84,62°, γ( = 63,63°) 相似文献
19.
Cobalt bis(oxalato)nickelate pentahydrate, Co[Ni(C2O4)2]5H2O and cadmium bis(oxalato)nickelate tetrahydrate, Cd[Ni(C2O4)2]4H2O have been synthesized and characterized by elemental analysis, reflectance and IR spectral studies. Thermal decomposition
studies (TG, DTG and DTA ) in air showed that both the compound of cobalt and cadmium produced the oxide, MNiOx (x=3 for M=Co; x=2 for M=Cd ) at 325 and 360°C respectively. DSC studies in nitrogen attributed only the mixture of both the metal at the end.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
20.
E. A. Shusharina S. P. Khranenko P. E. Plusnin T. Yu. Kardash S. A. Gromilov 《Journal of Structural Chemistry》2011,52(5):918-923
Crystal structures of [Co(NH3)5Cl]MoO4 and [Co(NH3)5Cl]WO4 complex salts are determined by single crystal X-ray diffraction. It is demonstrated for both salts that within the temperature range T = ?123?20°C there is a negative thermal expansion (about 0.26%) towards the c axis of the orthorhombic unit cell (Pnma space group). Thermal properties of the salts are investigated. The phase composition of the products obtained on heating the salts in different gas atmospheres is studied. 相似文献