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1.
The reversible equilibrium conversion under H 2 of [RuCl(dppb) (μ-Cl)] 2 (1) to generate (η 2-H 2) (dppb) (μ-Cl) 3RuCl(dppb) in CH 2Cl 2 (dppb = Ph2P( CH2) 4PPh2) has been studied at 0–25 °C by UV-Vis and 31P{ 1H} NMR spectroscopy, and by stoppe kinetics; the equilibrium constant and corresponding thermodynamic parameters, and the forward and reverse rate constants at 25 °C have been determined. A measured Δ H° value of 0 kJ mol −1 allows for an estimation of an exothermicity of 60 kJ mol −1 for binding an η 2-H 2 at an Ru(II) centre; a Δ S° value of 60 J mol −1 K −1 indicates that in solution 1 contain s coordinated CH 2Cl 2. The kinetic and thermodynamic data are compared to those obtained from a previously studied hydrogenation of styrene catalyzed by 1. Preliminary findings on related systems containing Ph 2P(CH 2) 3PPh 2 and (C 6H 11) 2P(C 6H 11) 2 are also noted. 相似文献
2.
The phosphinoalkenes Ph 2P(CH 2) nCH=CH 2 ( n= 1, 2, 3) and phosphinoalkynes Ph 2P(CH 2) n C≡CR (R = H, N = 2, 3; R = CH 3, N = 1) have been prepared and reacted with the dirhodium complex (η−C 5H 5) 2Rh 2(μ−CO) (μ−η 2−CF 3C 2CF 3). Six new complexes of the type (ν−C 5H 5) 2(Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3)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−CH 3C 5H 4)Mn(CO) 2thf resulted in coordination of the manganese to the alkene function. The Rh 2---Mn complex [(η−C 5H 5) 2Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3) {Ph 2P(CH 2) 3CH=CH 2} (η−CH 3C 5H 4)Mn(CO) 2] was fully characterized. Simi treatment of the dirhodium-phosphinoalkyne complexes with Co 2(CO) 8 resulted in the coordination of Co 2(CO) 6 to the alkyne function. The Rh 2---Co 2 complex [(η−C 5H 5) 2Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3) {Ph 2PCH 2C≡CCH 3}Co 2(CO) 2], C 37H 25Co 2F 6O 7PRh 2, 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 Rh 2 and Co 2 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 Rh 2 and perpendicular for Co 2. Attempts to induce Rh 2Co 2 cluster formation were unsuccessful. 相似文献
3.
The photochemistry of the diphosphino Pt(II) hydrides [LPtH 2] (L=(t-Bu) 2P(CH 2) 2P(t-Bu) 2 (7); L=(t-Bu) 2P(CH 2) 3P(t-Bu) 2 (8);L=(t-Bu)(Ph)P(CH 2) 2P(Ph)(t-Bu) (9)) is reported. The primary photoevent is the dissociation of H 2 and formation of the 14-e [LPt] species. These coordinatively unsaturated intermediates provide a versatile entry point into the C---H bond activation of hydrocarbons. [LPt] reacts with benzene in an oxidative addition reaction to yield [LPt(H)(C 6H 5)] complexes. The importance of the metal centre and ancillary ligation in the C---H bond activation is discussed. 相似文献
4.
Reactions of [Rh(COD)Cl] 2 with the ligand RN(PX 2) 2 (1: R = C 6H 5; X = OC 6H 5) give mono- or disubstituted complexes of the type [Rh 2(COD)Cl 2{ν 2−C 6H 5N(P(OC 6H 5) 2) 2}] or [RhCl{ν 2−C 6H 5 N(P(OC 6H 5) 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−C 6H 5N(P(OC 6H 5) 2) 2} 2, whereas the same reaction with 2 (R = CH 3; X = OC 6H 5) leads to the formation of an asymmetric complex of the type [Rh(CO)(μ−CO)Cl{μ−CH 3N(P(OC 6H 5) 2) 2} 2 containing both terminal and bridging CO groups. Interestingly the reaction of 3 (R = C 6H 5, X = OC 6H 4Br− p with either [Rh(COD)Cl] 2 or [Rh(CO) 2Cl] 2 leads only to the formation of the chlorine bridged binuclear complex, [RhCl{ν 2−C 6H 5N(P(OC 6H 4Br− 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
5.
The observation of homolytic S---CH 3 bond cleavage in (Ph 2P( o-C 6H 4)SCH 3) 2Ni 0 under photochemical conditions has prompted further investigation of nickel(0) complexes and their stability. Tetradentate P 2S′ 2 donor ligands (S′ = thioether type S donor) with aromatic rings incorporated into the P to S links, Ph 2P( o-C 6H 4)S(CH 2) 3S( o-C 6H 4)PPh 2 (arom-PSSP), or the S to S links, Ph 2P(CH 2) 2SCH 2( o-C 6H 4)CH 2S(CH 2) 2PPh 2 (PS-xy-SP), have been used to form four-coordinate, square planar nickel(II) complexes, [(arom-PSSP)Ni](BF 4) 2 (2) and [(PS-xy-SP)Ni](BF 4) 2 (3). The bidentate and tetradentate ligands, Ph 2P( o-C 6H 4)SCH 2CH 3 (arom-PSEt) and Ph 2P(CH 2) 2S(CH 2) 3S(CH 2) 2PPh 2 (PSSP), give similar complexes, [(arom-PSEt) 2Ni](BF 4) 2 (1) and [(PSSP)Ni](BF 4) 2 (4), respectively. Cyclic voltammograms of the Ni 11 complexes in CH 3CN show two reversible redox events assigned to
and
. The one-electron reduction product produced by stoichiometric amounts of Cp 2Co can be characterized by EPR. At 100 K rhombic signals show hyperfine coupling to two phosphorus atoms. Complete bulk chemical reduction of complexes 1, 2, 3 and 4 with Na/Hg amalgam provided the corresponding nickel(0) complexes 1 R, 2 R, 3 R and 4 R which were isolated as red solutions or solids characterized by magnetic resonance properties and reaction products. Photolysis of these nickel(0) complexes leads to S-dealkylation to produce alkyl radicals and dithiolate nickel(II) complexes. Complex 3 crystallized in the monoclinic space group P2t/ c with a=20.740(5), B=9.879(3), C=17.801(4) åA, ß=92.59(2)°, V=3644(2) Å 3 and Z=4; complex 4: P2 1/ c with A=13.815(4), B=13.815(4), C=15.457(5) åA, V=3365.4(14) Å 3 and Z=4. 相似文献
6.
A number of gallium(III) organophosphonates form adducts with the bidentate amines 2,2′-bipyridyl and 1,10-phenanthroline. These adducts contain a 1:2:1 molar ratio of metal/phosphorus/amine and have the proposed formulations Ga(O 3PR)(O 2P(OH)R)(C 10H 8N 2)·H 2O and Ga(O 3PR)(O 2P(OH)R)(C 12H 8N 2)·H 2O (where R=CH 3, C 6H 5 and CH 2C 6H 5; C 10H 8N 2 is 2,2′-bipyridyl and C 12H 8N 2 is 1,10-phenanthroline). Unlike the parent gallium(III) organophosphonates, which conform to the general formula Ga(OH)(O 3PR)· xH 2O ( x=0 or 1), the amine adducts lack the hydroxo group, but contain the organophosphonate ligand in the partially as well as fully deprotonated forms. All compounds were isolated from aqueous solutions as monohydrates, with the exception of the bipyridyl adduct of gallium(III) phenylphosphonate, which is anhydrous. TGA measurements suggest that for the hydrates, the water molecule is not coordinated to the metal. The bipyridyl adducts of gallium(III) phenylphosphonate and gallium(III) methylphosphonate, like the parent gallium(III) organophosphonates, are very likely layered, as indicated by the powder XRD patterns. In contrast, the corresponding phenanthroline adducts are non-layered, and both the bipyridyl and phenanthroline adducts of gallium(III) benzylphosphonate are amorphous solids. FTIR, powder XRD, TGA, XPS, solid state 31P/ 13C MAS-NMR and BET surface area data are presented and discussed. 相似文献
7.
The mixture of isomers of silylated cyclopentadiene derivative C 5H 5CH 2CH 2Si(OMe) 3 (1) has been used for the syntheses of the mononuclear Rh(I) complexes [η 5-C 5H 4(CH 2) 2Si(OMe) 3]Rh(CO) 2 (3). [η 5-C 5H 4(CH 2) 2Si(OMe) 3]Rh(COD) (4) and [η 5-C 5H 4(CH 2) 2Si(OMe) 3]Rh(CO)(PPh 3) (5). Upon entrapment of 3–5 in silica sol-gel matrices, air stable, leach-proof and recyclable catalysts 6–8 resulted. Their catalytic activities in some hydrogenation processes were compared with those of the non-immobilized complexes 3–5, as well as with those of homogeneous and heterogenized non-silylated analogs, 9–14. 相似文献
8.
Reaction of [Au(η 2-Ar){CH 2C(O)R}Cl] (Ar=C 6H 4N=N- Ph- 2, R=Me, C 6H 2(OMe) 3-3′,4′,5′; Ar=C 6H 3(N=NC 6H 4Me- 4′)-2, Me-5, R=Me) with PPh 3 and NaClO 4·H 2O (1:2:1) at room temperature, leads to reductive elimination giving [Au(PPh 3) 2]ClO 4 and the corresponding carbon-carbon coupling product ArCH 2C(O)R. A similar process takes place when complexes [Au(η 2-Ar){CH 2C(O)R}(PPh 3)Cl] are refluxed in tetrahydrofuran, through elimination of [Au(PPh 3)Cl]. 相似文献
9.
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
10.
Cp #2Yb (Cp #=C 5H 4(CH 2) 2NMe 2) has been obtained by reaction of YbI 2(THF) 2 with 2 equiv. of C 5H 4(CH 2CH 2NMe 2)K in THF. The X-ray structure analysis shows a bent structure with intramolecular coordination of both nitrogen atoms to ytterbium. The reaction of C 60-fullerene with Cp #2Yb leads to the formation of the fullerenide derivative [Cp #2Yb] 2C 60, which shows an ESR signal in the solid state and in THF solution at room temperature (solid: Δ H = 50 G, G = 1.9992; solution: Δ H = 10 G, G = 2.0001) and a magnetic moment of 3.6 BM. The lutetium fullerenides CpLu(C 60)(DME) (3) and Cp *Lu(C 60)(DME)(C 6H 5CH 3) (4), (Cp = η 5−C 5H 5, Cp * = η 5−C 5Me 5), were obtained by reaction of C 60 with CpLu(C 10H 8) (DME) and Cp *Lu(C 10H 8) (DME) in toluene. Both complexes are paramagnetic (μ eff = 1.4 and 0.9 BM) and exhibit temperature-dependent ESR signals (293 K: g = 1.992 and 2.0002 respectively). 相似文献
11.
The cyclopentadienyl osmium(II) complexes [(η 5-C 5H 5)Os(PPh 3) 2X] [X = Br (1), CH 3CN (2)] reacts with sodium azide (NaN 3) to yield the corresponding azido complex [(η 5-C 5H 5)Os(PPh 3) 2N 3] (3). This undergoes [3+2] dipolar cycloaddition reaction with activated alkynes like dimethyl and diethyl acetylenedicarboxylate to yield triazolato complexes [(η 5-C 5H 5)Os(PPh 3) 2{N 3C 2(CO 2R) 2}] [R = –CH 2CH 3 (4) and –CH 3 (5)]. The complex 3 also reacts with nitriles such as tetracyanoethylene (TCE), fumaronitrile and p-nitrobenzonitrile to yield complexes of the type [(η 5-C 5H 5)Os(PPh 3) 2{N 4C 2(CN)C(CN) 2}] (6), [(η 5-C 5H 5)Os(PPh 3) 2{N 3C 2HCN}] (7) and [(η 5-C 5H 5)Os(PPh 3) 2{N 4C(C 6H 4– p-NO 2)}] (8). These complexes were fully characterized on the basis of microanalyses, FT-IR and NMR spectroscopic data. The molecular structure of the representative complex [(η 5-C 5H 5)Os(PPh 3) 2{N 3C 2(CO 2CH 2CH 3) 2}] (4) was determined by single crystal X-ray analysis. 相似文献
12.
The binuclear cyanoferrate, tetraphenylphosphonium pentacyanoiron(III)-μ-cyano-amminetetracyanoiron(III), [(C 6H 5) 4P] 4[Fe 2(CN) 10NH 3] 4−, was synthesized by air oxidation of aqueous solutions of Na 3[Fe(CN) 5NH 3] · 3H 2O. Single crystal X-ray diffraction studies show the compound to contain the binuclear, cyano-bridged anion, [(NC) 5Fe---NC---Fe(CN) 4NH 3] 4−. This compound is structurally identical to the one prepared by A. Ludi et al., [Inorg. Chim. Acta, 34, 113 (1979)], with the exception that [Fe(CN) 6] 3− is not required for the synthesis of this compound. The Fe(III) atoms are antiferromagnetically coupled through the CN − bridge, as shown by a maximum in the magnetic susceptibility at 50 K. The electronic and IR spectra of the complex in the solid state and in solution are discussed. 相似文献
13.
The trinuclear complexes [Ag(PR 3) 2] 2[Ni(mnt) 2] and [AgL] 2[Ni(mnt) 2] have been prepared by reactions of (NEt 4) 2[Ni(mnt) 2] and Ag 2SO 4 with alkyl phosphines (PR 3=P(CH 3) 3 (PMe 3) for 1, P(C 2H 5) 3 (PEt 3) for 2 and P(C 6H 11) 3 (PCy 3) for 3), or with chelating diphosphines (L=1,1′-bis(diphenylphosphino)ferrocene (dppf) for 4 and bis(diphenylphosphino)methane (dppm) for 5). The structures of all the complexes have been determined by X-ray crystallography. Interactions between the [Ag(PR 3) 2] + and [Ni(mnt) 2] 2− groups occur in compounds 1 and 2 with Ni---Ag distances of 3.063(4) and 2.9311(6) Å, respectively. Only one sulfur atom of each mnt ligand bridged [Ag(PR 3) 2] + cations and [Ni(mnt) 2] 2− anions in compound 1 through 3 with Ag---S distances of about 2.7 Å. There is no interaction between Ag and Ni in compound 3 due to the flexibility of the cyclohexyl groups. Interactions between [AgL] + and [Ni(mnt) 2] 2− groups also occur in compound 4 with a much shorter Ag---Ni distance of 2.7213(7) Å, while silver atoms and the NiS 4 plane in compound 4 make a chair conformation with Ag---S distances of about 2.8 Å. In compound 5, dppm bridges two silver atoms, and interaction between silver atoms occurs at a distance of 2.9859(11) Å, and only one sulfur atom of mnt is used to bridge Ni and Ag atoms with Ag---S distances of 2.582(3) and 2.663(3) Å. 相似文献
14.
Using thermal and photochemical methods a series of new chromium complexes has been prepared: (ν 6- p-C 6H 4F 2)Cr(CO) 3; (ν 6-C 6H 5CF 3)Cr(CO) 3; [ m-C 6H 4(CF 3) 2]Cr(CO) 3; (ν 6-C 6H 5F)Cr(CO) 2H(SiCl 3); (ν 6-C 6H 5F)Cr(CO) 2(SiCl 3) 2; ( p-C 6H 4F 2)Cr(CO) 2-H(SiCl 3); (C 6H 5CF 3)Cr(CO) 2H(SiCl 3( p-C 6H 4F 2)Cr(CO) 2(SiCl 3) 2; C 6H 5CF 3)Cr(CO) 2(SiCl 3) 2; [ m-C 6H 4(CF 3) 2]Cr(CO) 2-H(SiCl 3); [ m-C 6H 4(CF 3) 2]Cr(CO) 2(SiCl 3) 2. Two compounds were structurally characterized by X-ray diffraction. These data combined with IR and 1H NMR have allowed assessment of some of the electronic and steric effects. The Cr-arene bond is considerably longer in the Cr(II) derivatives than in the Cr(0) species. Also the Cr center, as might be expected, is less electron rich in the Cr(II) dicarbonyl disilyl derivatives. The ν 6- p-C 6H 4F 2 ligands are slightly folded so that the C---F carbons are moved further away from the Cr center. Comparison of structural and electronic effects is made with a series of similar chromium compounds reported in the literature. These new (arene)Cr(II) derivatives possess more labile ν 6-arene ligands, which promise a rich chemistry at the chromium center. 相似文献
15.
A series of cationic nickel complexes [(η 3-methally)Ni(PP(O))]SbF 6 (1–4) [PP(O) = Ph 2P(CH 2)P(O)Ph 2 (dppmO) (1), Ph 2P(CH 2) 2P(O)Ph 2 (dppeO) (2), Ph 2P(CH 2) 3P(O)Ph 2 (dpppO) (3), pTol 2P(CH 2)P(O) pTol 2 (dtolpmO) (4)] has been synthesized in good yields by treatment of [(η 3-methally)NiBr] 2 with biphosphine monoxides and AgSbF 6. The ligands are coordinated in a bidentate way. Starting from [(η 3-all)PdI] 2 the cationic complexes [(η 3-all)PP(O))]Y (8–14). [PP(O) = dppmO, dppeO, dpppO, dtolpmO;Y = BF 4, SbF 6, CF 3SO 3, pTolSO 3] were synthesized in good yields. The coordination mode of the ligand is dependent on the backbone and the anion, revealing a monodentate coordination with dppmO for stronger coordinating anions. The intermediates [(η 3-all)Pd(I)(PP(O)-κ 1- P)] (5–7) [PP(O) = dppmO (5), dppeO (6), dtolpmO (7)] were isolated and characterized. Neutral methyl complexes [(Cl)(Me)Pd(PP(O))] (15–18). [PP(O) = dppmO (15), dppeO (16), dpppO (17), dtolpmO (18)] can easily be obtained in high yields starting from [(cod)PdCl 2]. For dppmO two different routes are presented. The structure of [(Me)(Cl)Pd{;Ph 2P(CH 2-P(O)Ph 2-κ 2- P, O};] · CH 2Cl 2 (15) with the chlorine atom trans to phosphorus was determined by X-ray diffraction. 相似文献
16.
Three new crystalline tin selenide salts have been prepared from the reactions of [PPh 4] 2[Sn(Se 43] in supercritical solvents. The starting material pyrolyzes in supercritical acetonitrile to form [PPh 4] 4[Sn 6Se 21] (I), and it also reacts with SnSe in supercritical ammonia leading to a mixture of [PPh 4] 4[Sn 3Se 11] 2 (II). and [PPh 4] 2[Sn(Se 4)(Se 6) 2] (III). All three compounds have been characterized by single crystal X-ray diffraction. Crystallographic data: for I, C 96H 90P 4Se 21Sn 6, space group triclinic, P-1, A = 18.763(3), B = 24.600(4), C = 13.137(1) Å, = 102.63(1), β = 93.66(1), γ = 108.72(1)°, V = 5544(1) Å 3, Z = 2, R = 0.0350, RW = 0.0317: for II, C 96H 80P 4Se 22Sn 6, space group monoclinic P2 1/ c, A = 31.500(4), B = 16.572(3), C = 22.352(3) Å, β = 103.53(1)°, V = 11344(3) Å 3, Z = 4, R = 0.0771, RW = 0.0664: for III, C 48H 40P 2Se 16Sn, space group monoclinic, C2/ c, A = 25.381(2), B = 13.934(4), C = 19.465(3) Å, β = 121.587(8)°, V = 5867(2) Å 3, Z = 4, R = 0.0807, RW = 0.0650. One of the compounds, [PPh 4] 2[Sn(Se 4(Se 62], is a molecular cluster while the other two complexes [PPh 4] 4[Sn 3Se 11] 2 and [PPh 4] 4[Sn 6Se 21], are one dimensional tin selenide chains. The structures of the two chains are related and consits of tetrahedral and distorted trigonal bipyramidal tin(IV) centers bridged by Se 2−, Se 22− and Se 32− chains. 相似文献
17.
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
18.
New mixed metal complexes SrCu 2(O 2CR) 3(bdmap) 3 (R = CF 3 (1a), CH 3 (1b)) and a new dinuclear bismuth complex Bi 2(O 2CCH 3) 4(bdmap) 2(H 2O) (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 SrF 2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi 2O 3 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), −2 J = 34.0(8) cm −1. Crystal data for 1a: C 27H 51N 6O 9F 9Cu 2Sr/THF, monoclinic space group P2 1/ m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å 3, Z = 2; for 1b: C 27H 60N 6O 9Cu 2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å 3, Z = 8; for 2: C 22H 48O 11N 4Bi 2, monoclinic space group P2 1/ c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å 3, Z = 4. 相似文献
19.
The reaction of [Re(NMe)Cl 3(PPh 3) 2] with the pentadentate [N 3S 2] ligand pyN 2H 2S 2---H 2 [2,6-bis(2-mercaptophenylamino)dimethylpyridine] (1) in the presence of triethylamine did not yield the anticipated six-coordinate complex [Re(NMe)(η 5-pyN 2HS 2)] (2), but rather resulted in cleavage of the Re(V)=NMe bond. A novel six-coordinate Re(IV) [N 3S]/[NS] complex [Re(η 4-SC 6H 4---2-NCH 2---C 5H 3N---C=NC 6H 4---2-S)(η 2-NHC 6H 4---2-S)] (4) was thus obtained with the simultaneous coordination of 2-aminothiophenol, a dianionic bidentate [NS] donor resulting from the decomposition of the parent ligand and ligand 3, a dianionic tetradentate [N 3S] donor formed by partial self-condensation and subsequent oxidation of the parent ligand 1. Crystal data for 4: C 25H 18N 4S 3Re·CH 2Cl 2, monoclinic, space group P2 1/ n, a=9.255(2) Å, b=11.181(2) Å, c=25.316(4) Å, β=97.434(3)°, V=2587.8(7) Å 3 and Z=4. 相似文献
20.
The reaction of perrhenate with 2-hydrazinopyrimidine in MeOH–HCl yields [ReCl 3(η 1-NNC 4H 3N 2H)(η 2-HNNC 4H 3N 2)] (1). The analogous reaction with Na 2MoO 4 yields [MoCl 3(η 1-NNC 4H 3N 2H)(η 2-HNNHC 4H 3N 2)] (1a). The reaction of 1 with pyrimidine-2-thiol and triethylamine produces [Re(η 1-C 4H 3N 2S)(η 2-C 4H 3N 2S)(η 1-NNC 4H 3N 2)(η 2-HNNC 4H 3N 2)] (2), while reaction of 1 with the Schiff base HSC 6H 4N=C(H)C 6H 4OH provides [Re(η 3-SC 6H 4N=C(H)C 6H 4O)(η 1-NNC 4H 3N 2)(η 2-HNNC 4H 3N 2)]·0.6CH 2Cl 2 (3·0.6CH 2Cl 2). The analogous hydrazinopyridine complex of the Schiff base, [Re(η 3-SC 6H 4N=C(H)C 6H 4O)(η 1-NNC 5H 4N)(η 2-HNNC 5H 4N)] (4), was also synthesized by reacting [ReCl 3(η 1-NNC 5H 4NH)(η 2-HNNC 5H 4N)] with HSC 6H 4N=C(H)C 6H 4OH. The crystal structures of 1–4 have been determined. 相似文献
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