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1.
2
,5
-1,3-Dithianes of the type (CH 3)C-CH(CH 2S) 2CH-C 6H 4-CC-R (R = CO 2H, CH 2CH 2CO 2H and CH 2CH 2PO 3H 2) are potent blockers of the GABA-gated chloride channel with 50% inhibition at 5–10 nM. Functionalization of the acid moieties provides candidate photoaffinity ligands [R = C(O)CHN 2 and CH 2CH 2C(O)CHN 2], affinity columns, and hapten-protein conjugates for antibody production. 相似文献
2.
5 e-tert-Butyl-2 e-[4-(substituted-ethynyl)phenyl]-1,3-dithianes with selected functional groups (R) on the ethynyl moiety are potent blockers of the GABA-gated chloride channel measured as inhibitor concentration (IC 50) for 4- n-[ 3H]propyl-1-(4-ethynylphenyl)-2, 6,7-trioxabicyclo[2.2.2]octanebinding to bovine brain membranes. The terminal R substituents were introduced by coupling 5 e-tert-butyl-2 e-(4-iodophenyl)-1,3-dithiane with HC ≡ CR or 5 e-tert-butyl-2 e-(4-ethynylphenyl)-1,3-dithiane with XR. The potency of the parent compound (R=H) with an IC 50 of 21 μM is equaled or exceeded by up to 7-fold (i.e. IC 50 = 3–21 μM) by several carboxylic acids [R = (CH 2) nCO 2H ( n = 0–3), (CH 2nOCH 2CO 2H ( n = 1–3) and CH 2SCH 2 CO 2H] and their esters and two phosphonic acids (CH 2CH 2PO 3H 2 and CH 2OCH 2PO 3H 2) but not their esters. These carboxyl and phosphonic acids (and their salts) include the most potent water-soluble chloride channel blockers known. Conversion to the monosulfones increases activity of the R = H and CH 2OH analogs by 1.2- to 3-fold but decreases that of the R = CH 2CH 2CO 2R′ (R′ = H or CH 3) derivatives by 3- to 13-fold. Quantitative structure-activity analyses for 44 2-[4-(substituted-ethynyl)phenyl]-dithianes suggests that the principal feature of the R substituent for high activity is its polarizable volume modeled as molecular refractivity, i.e. this substituent is not a well-defined pharmacophore and undergoes a structurally non-specific interaction with the receptor. These observations lay the background for preparing candidate affinity probes. 相似文献
3.
Condensation of Z-PPh 2CH 2C(Bu t)=NNH 2 with 4-nitroacetophenone gave the azine phosphine Z,E-PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4) (I). The corresponding phsophine oxide II was prepared by treatment of I with H 2O 2. The phosphine I with [Mo(CO) 4(nbd)] (nbd=norbornadiene) gave [Mo(CO) 4{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4)}] (1a); the corresponding tungsten 1b and chromium 1c complexes were made similarly. The crystal structure of 1a was determined by X-ray diffraction and showed the presence of a six-membered chelate ring with the bulky 4-nitrophenyl group held close to the metal. Oxidation of 1a with bromine gave the seven-coordinate molybdenum (II) complex 2. Treatment of [PtMe 2(cod)] (cod=cycloocta-1,5-diene) with I at 20°C gave the dimethyl-platinum (II) complex [PtMe 2{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4)}] (3a) which with MeI gave the iodotrimethylplatinum(IV) complex 4. Treatment of 3a with C≡O opened the chelate ring to give the dimethyl(carbonyl)platinum(II) complex 5 containing a monodentate phosphine ligand. When 3a was heated in toluene solution at 110°C it gave the cyclometallated methylplatinum(II) complex [PtMe{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 3NO 2-4)}] (6). Treatment of 6 with MeI gave the platinum(IV) complex 7. The dichloropalladium(II) complex [PdCl 2{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4)}] (3b) was prepared by treatment of [PdCl 2(NCPh) 2] with I in CH 2Cl 2. Treatment of [PtCl 2(NCMe) 2] with 2 equiv. of I gave the trans-bis(phosphine) complex 8. When 2 equiv. of I were treated with [PtCl 2(cod)] followed by NH 4PF 6 this gave the salt 9a containing two six-membered chelate rings; the analogous palladium(II) 9b) salt was also prepared. Treatment of 2 equiv. of I with [PtCl 2(cod)] followed by NH 4PF 6 gave the PF 6 salt 10 containing a six-membered chelate ring and a monodentate ligand. When 10 was treated with AgNO 3 followed by NH 4PF 6 this gave the bis-chelate complex 11 containing five- and six-membered chelate rings. Treatment of [IrCl(CO) 2( p-toluidine)] with I gave the cyclometallated iridium(III) hydride complex [IrHClCO{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 3NO 2-4)}] (12). [RuCl 2(PPh 3) 3] with the phosphine I resulted in the Ru(II) complex 13 in which the ortho hydrogens of the 4-nitrophenyl group are agostically interacting with ruthenium. Proton, Phosphorus-31, some carbon-13 NMR and IR data have been obtained. Crystals of 1a are orthorhombic, space group Pna2 1, with a = 1819.3(2), b = 1050.0(1), c = 1614.8(2) pm and Z = 4; final R = 0.0191 for 2616 observed reflections. 相似文献
4.
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
5.
The noncompetitive blocker (NCB) site of the γ-aminobutyric acid (GABA)-gated chloride channel is the target for many important insecticides and potent convulsants. This site is specifically blocked by 3H ethynylbicycloorthobenzoate ( 3H EBOB) and other trioxabicyclooctane radioligands and might be suitable for affinity probes with an appropriate heterocyclic substituent and linker moiety. Optimal potency at the NCB site is achieved with 5 e- tert-butyl-2 e-[4-(substituted-ethynyl)phenyl]-1,3-dithianes compared with analogs in which the butyldithiane portion is replaced with butyldithiane-sulfoxide or -sulfone, n-propyltrioxabicyclooctane or dioxatricyclododecene. Three positions were examined for coupling the linker and dithiane: C-2 of the dithiane; a branched substituent within the alkynyl moiety; the terminus of a straight chain extension from the ethynyl group, which proved to be the best. Optimized linkers for addition to the ethynylphenyldithiane to achieve appropriate length and fit within the active site, i.e. receptor potency, are CH 2OCH 2C(O)SCH 2CH 2(SH or NH 2) and the corresponding thiolates and amides. Several compounds with these spacers block the chloride channel, measured as inhibition of 3H EBOB binding, at 4–50 nM. 相似文献
6.
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
7.
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
8.
Addition of (Me 3SiNHCH 2CH 2) 2NH (H 3[N 3(TMS)]) or (Me 3SiNH- o-C 6H 4) 2NH (H 3[ArN 3(TMS)]) to a solution of TaMe 5 yields [N 3(TMS)]TaMe 2 or [ArN 3(TMS)]TaMe 2, respectively. An X-ray study of [ArN 3(TMS)]TaMe 2 showed it to have an approximate trigonal bipyramidal structure in which the two methyl groups are in equatorial positions and the triamido ligand is approximately planar. Addition of (C 6F 5NHCH 2CH 2) 2NH (H 3[N 3(C 6F 5)]) to TaMe 5 yields first [(C 6F 5NCH 2CH 2) 2NH]TaMe 3, which then decomposes to [(C 6F 5NCH 2CH 2) 2N]TaMe 2. An X-ray study of [(C 6F 5NCH 2CH 2) 2N]TaMe 2 shows it to be approximately a trigonal bipyramid, but the C 6F 5 rings are oriented so that they lie approximately in the TaN 3 plane and two ortho fluorines interact weakly with the metal. Trimethylaluminum attacks the central nitrogen atom in [N 3(TMS)]TaMe 2 to give [(Me 3SiNCH 2CH 2) 2NAlMe 3]TaMe 2, an X-ray study of which shows it to be a trigonal bipyramidal species similar to the first two structures, except that the C-Ta-C bond angle is approximately 30° smaller (106.6(12)°). Addition of B(C 6F 5) 3 to [(C 6F 5NCH 2CH 2) 2NH]TaMe 3 yields {[(C 6F 5NCH 2CH 2) 2NH]TaMe 2} + {B(C 6F 5) 3Me} −, the structure of which most closely resembles that of [(Me 3SiNCH 2CH 2) 2NAlMe 3]TaMe 2 in that the C-Ta-C angle is 102.0(6)°. The C 6F 5 rings in {[(C 6F 5NCH 2CH 2) 2NH]TaMe 2} + are turned roughly perpendicular to the TaN 3 plane, i.e. ortho fluorines do not interact with the metal in this molecule. 相似文献
9.
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
10.
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
11.
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
12.
Two new dicyanamide bridged 1D polynuclear copper(II) complexes [Cu(L 1){μ 1,5-N(CN) 2}] n (1) [L 1H = C 6H 5C(O)NHNC(CH 3)C 5H 4N] and [Cu(L 2){μ 1,5-N(CN) 2}] n (2) [L 2H=C 6H 5C(O)CHC(CH 3)NCH 2CH 2N(CH 3) 2] have been synthesised and structures of both the complexes and their crystal packing arrangements have been established by X-ray crystallography. For complex 1, a tridentate hydrazone ligand (L 1H) obtained by the condensation of benzhydrazide and 2-acetylpyridine is used, whereas a tridentate Schiff base (L 2H) derived from benzoylacetone and 2-dimethylaminoethylamine is employed for the preparation of complex 2. Variable temperature magnetic susceptibility measurement studies indicate there are weak antiferromagnetic interactions with J values −0.10 and −1.41 cm −1 for 1 and 2, respectively. 相似文献
13.
A series of borane and monoiodoborane derivatives of bis(diphenylphosphino)alkanes. (C 6H 5) 2P--- (CH 2) n---P(C 6H 5) 2 in which n has values of 2 through 4 has been synthesized. Only compounds with the formulae [(C 6H 5) 2P] 2(CH 2) n · (BH 3) 2 and (C 6H 5) 2P] 2CH 2) n · BH 2I were isolable, the latter being boronium iodides. The compounds were characterized by their melting points, elemental analyses, molar conductivities, infrared spectroscopy, and 1H and 11B nuclear magnetic resonance spectroscopy. The relationship between the length of the carbon chain and the 11B NMR chemical shift is discussed. 相似文献
14.
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
15.
The fluorinated thioether compounds [C 6H 4Br-2-(CH 2SR F)] (SR F = SC 6F 5 (1), SC 6F 4-4-H (2), SC 6H 4-2-F (3), SC 6H 4-3-F (4), SC 6H 4-4-F (5)) were synthesized and the reactivity of (1) was explored with transition metal complexes of the group 10. The results obtained indicate that the reactivity of these ligands is strongly dependent on the oxidation state of the metal center on the complex. Thus, products of the coordination of Pd(II) and Pt(II) to the sulfur moiety were obtained and unequivocally characterized by single crystal X-ray diffraction analyses. While spectroscopic evidence indicates that reaction of the Pt(0) compound [Pt(PEt 3) 3] leads to the formation of C–Br activation products, it is worth noting that similar reactions with Ni(0) and Pd(0) compounds only afford complex mixtures that in most of the cases indicate desulfurization of the ligands and decomposition of the metallic starting materials. 相似文献
16.
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
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.
Two novel, weakly antiferromagnetically coupled, tetranuclear copper(II) complexes [Cu 4(PAP) 2(μ 2-1,1-N 3) 2(μ 2-1,3-N 3) 2(μ 2-CH 3OH) 2(N 3) 4 (1) (PAP = 1,4-bis-(2′-pyridylamino)phthalazine) and [Cu 4(PAP3Me) 2 (μ 2-1,1-N 3) 2(μ 2-1,3-N 3) 2(H 2O) 2(NO 2) 2]- (NO 3) 2 (2) (PAP3Me = 1,4-bis-(3′-methyl-2′-pyridyl)aminophthalazine) contain a unique structural with two μ 2-1,1-azide intramolecular bridges, and two μ 2-1,3-azide intermolecular bridges linking pairs of copper(II) centers. Four terminal azide groups complete the five-coordinate structures in 1, while two terminal waters and two nitrates complete the coordination spheres in 2. The dinuclear complexes [Cu 2(PPD)(μ 2-1,1-N 3)(N 3) 2(CF 3SO 3)]CH 3OH) (3) and [Cu 2(PPD)(μ 2-1,1-N 3)(N 3) 2(H 2O)(ClO 4)] (4) (PPD = 3,6-bis-(1′-pyrazolyl)pyridazine) contain pairs of copper centers with intramolecular μ 2-1,1-azid and pyridazine bridges, and exhibit strong antiferromagnetic coupling. A one-dimensional chain structure in 3 occurs through intermolecular μ 2-1,1-azide bridging interactions. Intramolecular Cu-N 3-Cu bridge angles in 1 and 2 are small (107.9 and 109.4°, respectively), but very large in 3 and 4 (122.5 and 123.2°, respectively), in keeping with the magnetic properties. 2 crystallizes in the monoclinic system, space group C2/ c with a = 26.71(1), b = 13.51(3), c = 16.84(1) Å, β = 117.35(3)° and R = 0.070, Rw = 0.050. 3 crystallizes in the monoclinic system, space group P2 1/ c with a = 8.42(1), b = 20.808(9), c = 12.615(4) Å, β = 102.95(5)° and R = 0.045, Rw = 0.039. 4crystallizes in the triclinic system, space group P1, with a = 10.253(3), b = 12.338(5), c = 8.072(4) Å, = 100.65(4), β = 101.93(3), γ = 87.82(3)° and R = 0.038, Rw = 0.036 . The magnetic properties of 1 and 2 indicate the presence of weak net antiferromagnetic exchange, as indicated by the presence of a low temperature maximum in χ m (80 K (1), 65 K (2)), but the data do not fit the Bleaney-Bowers equation unless the exchange integral is treated as a temperature dependent term. A similar situation has been observed for other related compounds, and various approaches to the problem will be discussed. Magnetically 3 and 4 are well described by the Bleaney-Bowers equation, exhibiting very strong antiferromagnetic exchange (− 2 J = 768(24) cm −1 (3); − 2 J = 829(11) cm −1 (4)). 相似文献
19.
Tantalaalkylidene compounds, CHR=TaCl 3L 2 (R= tBu or CMe 2Ph, L=THF or 1/2dimethoxyethane) mixed with the cyclopalladated dimer [Pd(2-C 6H 4CH 2NMe 2)(μ-Cl)] 2, 1, afford good yields of heterodimetallic complexes [Pd(2-C 6H 4CH 2NMe 2)(μ-Cl)(μ-CHR=TaCl 3L], 3a, 3b, in which the Ta=C unit is η 2-interacting with the palladium atom, while a chloride ligand is bridging the tantalum and the palladium atoms. These compounds are fairly stable in air in the solid state and also in solution at RT. The interaction of the Ta=C unit with Pd in these bimetallic compounds is weak as shown by the ready formation of [Pd(2-C 6H 4CH 2NMe 2)PyCl] and CHR=TaCl 3Py 2 upon treatement with pyridine. Compounds analogous to 3a, b can also be obtained with 12 electrons tantalum complexes. Thus treating the same cyclopalladated dimer 1 with CHR=Ta(OAr) 3 (OAr=2,6-diisopropylphenyloxy) led to a much more stable though electron deficient species: [Pd(2-C 6H 4CH 2NMe 2)(μ-Cl)(μ-CH tBu=Ta(OAr) 3], 3c. Substitution in 3a of one chloride ion by an alkyl group occurred at the tantalum metal via reaction with ZnR 2 (R=---CH 2CMe 2Ph) leading to [Pd(2-C 6H 4CH 2NMe 2)(μ-Cl)(μ-CH tBu=TaCl 3(CH 2CMe 2Ph)], 4 for which there is no free rotation around the new Ta---C bond and in which one of the methylene protons is strongly interacting with the palladium centre. This compound is believed to mimic an intermediate to the formation of tantalacarbyne derivative, which was obtained earlier via reaction of the uncomplexed tantalacarbene compound with dialkylzinc compounds. 相似文献
20.
Mono- and bis(platinum) complexes containing N-alkyl-ethylenediamine units of the type { cis-PtCl 2[H 2NCH 2CH 2NH(CH 2) nCH 3]} ( n=8, 9, 11, 15) and [{ cis-PtCl 2(H 2NCH 2CH 2NH)} 2(CH 2) n] ( n=6, 8, 10, 12) and their corresponding dihydroxo-platinum(IV) complexes were synthesized. The structures of the metal chelates were derived from elemental analyses and their 1H, 13C, IR spectra. The length of the aliphatic chains has been varied systematically, in order to increase the lipophilicity. Enlargement of the linker could also lead to more flexibility of one platinum sphere in reference to the attached DNA species. Using in vitro cytotoxicity tests it is shown that the biological activity of the bis(platinum) complexes increased, up to n=12, with the length of the linker. The longest linker in the ligands resulted in the most effective bis(platinum) complexes against L1210 murine leukemia cells. 相似文献
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