共查询到20条相似文献,搜索用时 359 毫秒
1.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
2.
The reaction of [AuCl(PPh 3)] with Pb(SR) 2(R = C 2H 5, C 6H 5, CH 2C 6H 5, C 6F 5, C 6H 2Me 3-2,4,6, Pr i and Bu t) provides a clean method to obtain complexes of the type [Au(SR)(PPh 3)] in good yields. The new compounds have been characterized by IR, 1H, 31P, 19F and 31C NMR. A study by FAB mass spectrometry indicates that an ion-molecule aggregation process takes place. 相似文献
3.
Reaction of optically active ketone complexes (+)-( R)-[(η 5-C 5H 5)Re(NO)-(PPh 3)(η 1-O=C(R)(CH 3)] + BF 4− (R = CH 2CH 3, CH(CH 3) 2m C(CH 3) 3, C 6H 5) with K(s-C 4H 9) 3BH gives alkoxide complexes (+)-( RS)-(η 5-C 5H 5)Re(NO)(PPh 3)-(OCH(R)CH 3) (73–90%) in 80–98% de. The alkoxide ligand is then converted to Mosher esters (93–99%) of 79–98% de. 相似文献
4.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl 2(P-P)] (P-P = (PPh 3) 2, Ph 2P(CH 2) 3PPh 2, Phd 2P(CH 2) 4PPh 2; 1,4-dithiols = HS(CH 2) 4SH, (−)DIOSH 2 (2,3- O-isopropylidene-1,4-dithiol-l-threitol), BINASH 2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt 3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph 2P(CH 2) 3PPh 2, Ph 2P(CH 2) 4PPh 2; dithiolato = −S(CH 2) 4S −, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh 3) 2] and [Pd(S(CH 2) 4S)(Ph 2P(CH 2) 3PPh 2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC1 2 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl 2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%. 相似文献
5.
Two organogold derivatives of diphenylmethane and diphenylethane, Ph 3PAu( o-C 6H 4)CH 2(C 6H 4- o)AuPPh 3 (1) and Ph 3PAu( o-C 6H 4)(CH 2) 2(C 6H 4- o)AuPPh 3 (2), have been synthesized by the reaction of ClAuPPh 3 with Li( o-C 6H 4)CH 2(C 6H 4- o)Li and Li( o-C 6H 4)(CH 2) 2(C 6H 4- o)Li respectively. The interaction of 1 with dppe results in the replacement of the two PPh 3 groups to give a macrocyclic compound (3) that includes an Au Au bond. Compounds 1 and 2 react with one or two equivalents of [Ph 3PAu]BF 4 to form new types of cationic complex [CH 2(C 6H 4- o) 2(AuPPh 3) 3]BF 4 (4), [CH 2(C 6H 4- o) 2(AuPPh 3) 4](BF 4) 2 (5), and [(CH 2) 2(C 6H 4- o) 2(AuPPh 3) 4](BF 4) 2 (6). Complexes 1–6 have been characterized by X-ray diffraction studies, FAB MS, and IR as well as by 1H and 31P NMR spectroscopy. A complicated system of Au H-C agostic interactions, involving the bridging alkyl groups (—CH 2— and CH 2-CH 2—) of diphenylmethane and diphenylethane ligands, has been found to occur in complexes 1–3 and 6. 相似文献
6.
A new emissive mononuclear homoleptic Cu(I) complex of 5-tert-butyl-3-(6-methyl-2-pyridyl)-1H-1,2,4-triazole (bmptzH),[Cu(bmptzH) 2](ClO 4) (1), has been synthesized by treatment of [Cu(PPh 3) 2(CH 3CN) 2](ClO 4) or[Cu(CH 3CN) 4](ClO 4) with the bmptzH ligand. It is revealed that complex 1 displays a distorted N 4 tetrahedral arrangement formed by two bmptzH chelates, in which bmptzH adopts a neutral bidentate chelating coordination mode using the N atom of the pyridyl ring and the 4-N not 2-N atom of the 1,2,4-triazolyl ring. It is shown that complex 1 is highly stable and exhibits good luminescence properties in solution and solid states at room temperature due to the introduction of a methyl group at the ortho-position of the pyridyl ring. 相似文献
7.
The dialkynyl complexes cis-[Pt(C CR) 2L 2] [R = Ph, L 2 = 2PPh 3, 2PEt 3, dppe (dppe = 1,2-bis(diphenylphosphino)ethane]; R --- tBu, L 2 = 2PPh 3, dppe) react with silver perchlorate in a molar ratio 1:0.5 to give platinum-silver perchlorate salts of the type [Pt 2 Ag(C CR) 4L 4](ClO 4) in excellent yield. The X-ray crystal structure of [Pt 2Ag(C = CPh) 4(PPh 3) 4](ClO 4) 1 shows that the cation is formed by two nearly orthogonal cis-[Pt(C CPh) 2(PPh 3) 2] units connected through a silver cation which is unsymmetrically π-bonded to all four acetylene fragments. Similar reactions of cis-[Pt(C CR) 2L 2] with one equivalent of AgClO 4 afford cationic complexes of general formula [PtAg(C CR) 2L 2](ClO 4), which are believed to be salts, [Pt 2Ag 2(C CR) 4L 4](ClO 4) 2. 相似文献
8.
A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH 2O(CH 2CH 2O) nCH 2CH 2PPh 2) 2]PtCl 2 ( n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH 2O(CH 2CH 2O) nCH 2CH 2PPh 2) 2 ( n=1–3) (3a–c) and (PhCN) 2PtCl 2 under high dilution conditions in CH 2Cl 2. The bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1′-Fc(CH 2O(CH 2CH 2O) nCH 2CH 2OH) 2 ( n=1–3) (1a–c) with: (i) CH 3SO 2Cl in CH 2Cl 2 and (ii) LiPPh 2 in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg 2+, or NH 4+ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest complexes for 4a,b. In the case of 4c only the addition of Na + or K + leads to an insignificant effect. 相似文献
9.
The ruthenium(II) complex Ru(CO) 2(NH 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I has been prepared by the reaction of Ru(CO) 4(Si(C 6H 5)(CH 3) 2)I with benzylamine. Two-dimensional homonuclear 1H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO) 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I·1/3C 5H 12 (triclinic; P
; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest. 相似文献
10.
Two ligands [ortho-C6H4NR2(CH2NH)]2CH2CH2(3: R=Me; 4: R=EO were prepared by the reduction of preligands [ortho-C6H4NR2(CH=N)]zCH2CH2(1: R=Me; 2: R=Et). These ligands reacted with AIMe3 to afford the corresponding dinuclear aluminum complexes {A1Me2[ortho-C6H4NR2(CH2N)]}2CHzCH2(5: R=Me; 6: R=Et). All the compounds were characterized by 1H and UC nuclear magnetic resonance(NMR) spectroscopies and elemental analyses. The catalytic properties of the aluminum complexes towards the ring-opening polymerization of lactones were investi- gated in the presence of benzvl alcohol. All the oolvmerization reactions were proceeded in a controlled manner. 相似文献
11.
The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C 5Me 4CH 2PMe 2)], where M=Li + (1), Na + (2), or K + (3), and [Li(C 5H 4CR′ 2PMe 2)], where R′ 2=Me 2 (4), or (CH 2) 5 (5), [HC 5Me 4CH 2PMe 2H]X, where X −=Cl − (6) or PF 6− (7) and [HC 5Me 4CH 2PMe 2] (8), are described. They have been used to prepare new metallocene compounds, of which representative examples are [Fe(η-C 5R 4CR′ 2PMe 2) 2], where R=Me, R′=H (9); R=H and R′ 2=Me 2 (10), or (CH 2) 5 (11), [Fe(η-C 5H 4CMe 2PMe 3) 2]I 2 (12), [Fe{η-C 5Me 4CH 2P(O)Me 2} 2] (13), [Zr(η-C 5R 4CR′ 2PMe 2) 2Cl 2], where R=H, R′=Me (14), or R=Me, R′=H (15), [Hf(η-C 5H 4CMe 2PMe 2) 2]Cl 2] (16), [Zr(η-C 5H 4CMe 2PMe 2) 2Me 2] (17), {[Zr(η-C 5Me 4CH 2PMe 2) 2]Cl}{(C 6F 5) 3BClB(C 6F 5) 3} (18), [Zr{(η-C 5Me 4CH 2PMe 2) 2Cl 2}PtI 2] (19), [Mn(η-C 5Me 4CH 2PMe 2) 2] (20), [Mn{(η-C 5Me 4CH 2PMe 2B(C 6F 5) 3} 2] (21), [Pb(η-C 5H 4CMe 2PMe 2) 2] (23), [Sn(η-C 5H 4CMe 2PMe 2) 2] (24), [Pb{η-C 5H 4CMe 2PMe 2B(C 6F 5) 3} 2] (25), [Pb(η-C 5H 4CMe 2PMe 2) 2PtI 2] (26), [Rh(η-C 5Me 4CH 2PMe 2)(C 2H 4)] 29, [M(η,κ P-C 5Me 4CH 2PMe 2)I 2], where M=Rh (30), or Ir, (31). 相似文献
12.
Reaction of [18]aneS 6 with two molar equivalents of [Cu(NCMe) 4](ClO 4) in CH 2Cl 2-MeCN affords the binuclear copper(I) complex [Cu 2([18]aneS 6)(NCMe) 2](ClO 4) 2. The single crystal X-ray structure of the complex shows a centrosymmetric cation with two tetrahedral copper(I) centres each coordinated to three thioether S-donors of [18]aneS 6,Cu---S(1) = 2.3200(15), Cu---S(4) = 2.3415(16), Cu---S(7) = 2.3250(15) Å, and to one MeCN molecule, Cu---N(1) = 1.939(5) Å, to give an overall NS 3-donation at the metal centres. Additionally, S(7′) shows a long-range interaction, Cu …S(7′) = 3.318(2) Å thus distorting the coordination geometry of the metal ion towards trigonal bipyramidal. The metal-metal separation of 4.428(2) Å suggests that there is no significant interaction between the copper centres of the dimer. Reaction of [9]aneS 3 with one molar equivalent of [Cu(NCMe) 4](ClO 4) in refluxing MeCN in the presence of ligands, L, affords the adducts [Cu([9]aneS 3)L] + (L = PPh 3, AsPh 3). The single crystal X-ray structure of the complex [Cu([9]aneS 3)(AsPh 3)](ClO 4) shows tetrahedral AsS 3 coordination at copper(I) with [9]aneS 3 bound facially to the metal centre, Cu---S = 2.303(6), Cu---As = 2.322(4) Å. 相似文献
13.
RuRhH 2Cl(COD)(dppm) 2 (1) (COD = 1,5-C 8H 12, DPPM = Ph 2PCH 2PPh 2) does not react with LiBHEt 3 in THF, but in toluene RuRhH 2(PhPCH 2PPh 2)(dppm)(COD) (3) is formed quantitatively. In contrast, the reaction of 1 with KBH(sec-Bu) 3 in THF selectively gives RuRhH 2(CH(PPh 2) 2)(dppm)(COD) (4), whereas in toluene a mixture of 3 and 4 is obtained. Mechanisms are proposed for these reactions. The X-ray crystal structure of 4 · PhCH 3 reveals direct coordination of a methanido group to rhodium and a long metal-metal distance (3.3006(6) Å). 相似文献
14.
Organolanthanide chloride complexes [(CH 3OCH 2CH 2C 5H 4) 2Ln(μ-Cl)] 2 (Ln = La, Pr, Ho and Y) react with excess NaH in THF at 45°C to give the dimeric hydride complexes [(CH 3OCH 2CH 2C 5H 4) 2Ln(μ-H)] 2, which have been characterized by IR, 1H NMR, MS and XPS spectroscopy, elemental analyses and X-ray crystallography. [(CH 3OCH 2CH 2C 5H 4) 2Y(μ-H)] 2 crystallizes from THF/n-hexane at −30°C, in the triclinic space group P1 with a = 8.795(2) Å, b = 11.040(1) Å, c = 16.602(2) Å, = 93.73(1)°, β = 91.82(1)°, γ = 94.21(1)°, Dc = 1.393 gcm −3 for Z = 2 dimers. However, crystals of [(CH 3OCH 2CH 2C 5H 4) 2Ho(μ-OH)] 2 were obtained by recrystallization of holmium hydride in THF/n-hexane at −30°C, in the orthorhombic space group Pbca with a = 11.217(2) Å, b = 15.865(7) Å, c = 17.608(4) Å, Dc = 1.816 gcm −3 for Z = 4 dimers. In the complexes of yttrium and holmium, each Ln atom of the dimers is coordinated by two substituted cyclopentadienyl ligands, one oxygen atom and two hydrogen atoms (for the Y atom) or two hydroxyl groups (for the Ho atom) to form a distorted trigonal bipyramid if the C(η 5)-bonded cyclopentadienyl is regarded as occupying a single polyhedral vertex. 相似文献
15.
The complexes [Fe{η-C 5H 4---( E)---CH=CH---4-C 6H 4CCX} 2] [X=SiMe 3 (1), H (2), Au(PCy 3) (3), Au(PPh 3) (4), Au(PMe 3) (5), RuCl(dppm) 2 (7), RuCl(dppe) 2 (8)] and [Fe{η-C 5H 4---( E)---CH=CH---4-C 6H 4CH=CRuCl(dppm) 2} 2](PF 6) 2 (6) have been prepared and the identities of 1 and 7 confirmed by single-crystal X-ray structural studies. Complexes 1–8 exhibit reversible oxidation waves in their cyclic voltammograms attributed to the Fe II/III couple of the ferrocenyl groups, 6–8 also showing reversible (7, 8) or non-reversible (6) processes attributed to Ru-centered oxidation. Cubic nonlinearities at 800 nm by the Z-scan method are low for 1–5; in contrast, complexes 6 and 7 exhibit large negative γreal and large γimag values. A factor of 4 difference in γ and two-photon absorption cross-section σ2 values for 6 and 7 suggest that they have potential as protically switchable NLO materials. 相似文献
16.
The nucleophile [ArTe −] generated in situ borohydride solution of Ar 2Te 2, reacts with 2-(chloromethyl) tetrahydrofuran and 2-(2-bromoethyl)-1,3-dioxolane resulting in L 1 and L 2, respectively. The complexes of palladium(II) and platinum(II) with L 1/L 2 having stoichiometries [MCl 2·L 2], [ML 2](ClO 4) 2, [(DPPE)ML 2](ClO) 4) 2, [(PPh 3) 2ML 2](ClO 4) 2 and [(phen)ML 2](ClO 4) 2 (where L = L 1/L 2 DPPE = Ph 2PC H 2CH 2PPh 2, PHEN = 1,10-phenanthroline and M = Pd/Pt) have been synthesized. IR, 1H, 125Te{ 1H} and 31P{ 1H} NMR and UV-vis spectral data of these species in conjunction with their molar conductance and molecular weight data have been used to authenticate the new species. In all complexes (1–20) the ligands L 1 and L 2 are coordinated through tellurium and in the complexes of formula [ML 2](ClO 4) 2 (M = Pd, Pt) the ligand is bidentate with the oxygen atom used in complexation. In solution, complexes PtCl 2L 2 exist as a mixture of cis and trans isomers whereas only the trans isomer was observed for the palladium analogues. The [(phen)PdL 2](ClO 4) 2(Q) quenches 1O 2 readily. The plot of log [Q] vs time is linear. Mechanism compatible with the experimental observations is proposed. 相似文献
17.
The synthesis of cyclopentadienyl complexes containing polydentate C 5R 4(CH 2CH 2NMe 2) ligands (R = H, Me) and Group 13 elements (Al, Ga, In) is described. The compounds (C 5Me 4CH 2CH 2NMe 2) AlX 2 (X = Me, Cl, Br, I), (C 5Me 4CH 2CH 2NMe 2)MCl 2 (M = Ga, In), (C 5H 4CH 2CH 2NMe 2)AlX 2 (X = H, Me, Et, Cl), (C 5H 4CH 2- CH 2NMe 2)GaCl 2,and (C 5H 4CH 2CH 2NMe 2)InMe 2 are obtained by three different procedures. All compounds that have been characterized, so far, by X-ray diffraction studies show an additional intramolecular coordination of the nitrogen atom in the side chain. Monomeric structures and sufficient volatilities make them potential candidates for MOCVD processes. 相似文献
18.
The heterobimetallic trinuclear sulfido clusters [(Cp*Ir) 2(μ 3-S) 2MCl 2] (M=Pd (3), Pt (4); Cp*=η 5-C 5Me 5) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH) 2IrCp*Cl] (2) and [MCl 2(COD)] (COD=cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh 3) 4] afforded the cationic trinuclear cluster [(Cp*Ir) 2(μ 3-S) 2PdCl(PPh 3)]Cl (5). Clusters 3 and 4 reacted with PPh 3 to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir) 2(μ 3-S) 2M(dppe)][BPh 4] 2 (M=Pd (9), Pt (10); DPPE=Ph 2PCH 2CH 2PPh 2) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH 2Cl 2, 9·CH 3COCH 3, and 10·CH 3COCH 3 were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst. 相似文献
19.
The reaction (1 : 1) between [A
Me 2)Cl 2] and [Hg(2-C 6H 4-N=NPh) 2] gives the complex [(2-PhN=NC 6H 4)A
MeC 2)Cl], which on treatment with AgClO 4 gives [(2-Ph
Me 2)]ClO 4. From this complex, the species [(2-PhN=NC 6H 4)A
Me 2)X] (X = CH 3COO, CN), or [(2-PhN=NC 6H 4)A
Me 2)L] (L = PPh 3, py) are obtained by reaction with the corresponding KX salts or neutral ligands. The crystal structure of [(2-Ph
Me2)][AuCl4] (obtained by metathesis between the corresponding perchlorate and tetramethylammonium salts) has been determined; the cation displays square-planar coordination with two cis-nitrogen (Au---N: 2.166(15), 2.140(14) Å) and two cis-carbon (Au---C: 2.021(16), 2.033(17) Å) atoms bonded to the gold atom. 相似文献
20.
A study has been carried out of the catalytic activity of the systems formed by [HRh{P(OPh) 3} 4] or [HRh(CO){P(OPh) 3} 3] with the modifying ligands P(OPh) 3, PPh 3, diphos and Cp 2Zr(CH 2PPh 2) 2 in hydroformylation of hex-1-ene (at p = 5 bar). The best results were obtained with the system [HRh{P(OPh) 3} 4]+Cp 2Zr(CH 2PPh 2) 2 (75–85% yeild of aldehydes). 相似文献
|