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1.
Reaction of [(p-cymene)RuCl2(PPh3)] (1) or [CpMCl2(PPh3)] (Cp = C5Me5) (3a: M = Rh; 4a: M = Ir) with 1-alkynes and PPh3 were carried out in the presence of KPF6, generating the corresponding alkenyl-phosphonio complexes, [(p-cymene)RuCl(PPh3){CHCR(PPh3)}](PF6) (2a: R = Ph; 2b: R = p-tolyl) or [CpMCl(PPh3){CHCPh(PPh3)}](PF6) (5: M = Rh; 6: M = Ir). Similar reactions of complexes [CpRhCl2(L1)] (3a: L1 = PPh3; 3c: L1 = P(OMe)3) with L2 (L2 = PPh3, PMePh2, P(OMe)3) gave [CpRhCl(L1)(L2)](PF6) (7bb: L1 = L2 = PMePh2; 7ca: L1 = P(OMe)3, L2 = PPh3; 7cc: L1 = L2 = P(OMe)3). Alkenyl-phosphonio complex 5 was treated with P(OMe)3 or 2,6-xylyl isocyanide, affording [CpRhCl(L){CHCPh(PPh3)}](PF6) (8a: L = P(OMe)3; 8b: L = 2,6-xylNC). X-ray structural analyses of 2a, 6 and 8a revealed that the phosphonium moiety bonded to the Cβ atom of the alkenyl group are E configuration.  相似文献   

2.
The synthesis of bis-cyclometalated aminocarboxylato complexes [M(α-aminocarboxylato)(ptpy)2] (M = Rh, 3, 4, 5; M = Ir, 6, 7, 8), ptpy = 2-(p-tolyl)pyridinato; aminocarboxylato = glycinato, l-alaninato, l-prolinato) from [{M(μ-Cl)(ptpy)2}2] (M = Rh, 1; M = Ir, 2) is described. The molecular structure of [Ir(l-alaninato)(ptpy)2] (7) was confirmed by a single-crystal X-ray diffraction study. Compound 7 crystallized from methanol-iso-hexane in the space group P21. For 7 the two diastereoisomers ΔIr, SC and ΛIr, SC were found crystallizing twice per unit. Absorption and emission spectra were recorded. The rhodium compounds are weak yellow-green and the iridium species strong green emitters.  相似文献   

3.
Reactions of labile [MCl3(PPh3)2(NCMe)] (M = Tc, Re) precursors with 1H-benzoimidazole-2-thiol (H2L1), 5-methyl-1H-benzoimidazole-2-thiol (H2L2) and 1H-imidazole-2-thiol (H2L3), in the presence of PPh3 and [AsPh4]Cl gave a new series of trigonal bipyramidal M(III) complexes [AsPh4]{[M(PPh3)Cl(H2L1-3)3]Cl3} (M = Re, 1-3; M = Tc, 4-6). The molecular structures of 1 and 3 were determined by X-ray diffraction. When the reactions were carried out with benzothiazole-2-thiol (HL4) and benzoxazole-2-thiol (HL5), neutral paramagnetic monosubstituted M(III) complexes [M(PPh3)2Cl2(L4,5)] (M = Re, 8, 9; M = Tc, 10, 11) were obtained. In these compounds, the central metal ions adopt an octahedral coordination geometry as authenticated by single crystal X-ray diffraction analysis of 8 and 11. Rhenium and technetium complexes 1, 4 and rhenium chelate compounds 8, 9 have been also synthesized by reduction of [MO4] with PPh3 and HCl in the presence of the appropriate ligand. All the complexes were characterized by elemental analyses, FTIR and NMR spectroscopy.  相似文献   

4.
The synthesis, characterization, and application in asymmetric catalytic cyclopropanation of Rh(III) and Ir(III) complexes containing (Sa,RC,RC)-O,O′-[1,1′-binaphthyl-2,2′-diyl]-N,N′-bis[1-phenyl-ethyl]phosphoramidite (1) are reported. The X-ray structures of the half-sandwich complexes [MCl2(C5Me5)(1P)] (M = Rh, 2a; M = Ir, 2b) show that the metal-phosphoramidite bond is significantly shorter in the Ir(III) analog. Chloride abstraction from 2a (with CF3SO3SiMe3 or with CF3SO3Me) and from 2b (with AgSbF6) gives the cationic species [MCl(C5Me5)(1,2-η-1P)]+ (M = Rh, 3a; M = Ir, 3b), which display a secondary interaction between the metal and a dangling phenethyl group (NCH(CH3)Ph) of the phosphoramidite ligand, as indicated by NMR spectroscopic studies. Complexes 3a and 3b slowly decompose in solution. In the case of 3b, the binuclear species [Ir2Cl3(C5Me5)2]+ is slowly formed, as indicated by an X-ray study. Preliminary catalytic tests showed that 3a cyclopropanates styrene with moderate yield (35%) and diastereoselectivity (70:30 trans:cis ratio) and with 32% ee (for the trans isomer).  相似文献   

5.
[Rh(CO)2Cl]2 reacts with two mole equivalent of 2-acetylpyridine (a), 3-acetylpyridine (b) and 4-acetylpyridine (c) to afford chelate [Rh(CO)Cl(η2-N∩O)] (1a) and non-chelate [Rh(CO)2Cl(η1-N∼O)] (1b, 1c) complexes, where, N∩O = a, N∼O = b, c. Oxidative addition (OA) of 1a-1c with CH3I and C2H5I yields penta coordinate rhodium(III) complexes, [Rh(COR)ClI(η2-N∩O)] {R = -CH3 (2a); -C2H5 (3a)} and [Rh(COR)(CO)ClI(η1-N∼O)] {R = -CH3 (2b, 2c); -C2H5 (3b, 3c)}. Kinetic study for the reaction of 1a-1c with CH3I indicates a pseudo-first order reaction. The catalytic activity of 1a-1c for the carbonylation of methanol to acetic acid and its ester was evaluated at different initial CO pressures 5, 10 and 20 bar at ∼25 °C and higher turn over numbers (TON = 1581-1654) were obtained compared to commercial Monsanto’s species [Rh(CO)2I2] (TON = 1000) under the reaction conditions: temperature = 130 ± 1 °C, pressure = 15-32 bar, rpm = 450, time = 1 h and catalyst: substrate = 1: 1900.  相似文献   

6.
Phosphorus-carbon bond is formed via: (i) the apparent HCCH insertion into Ir-P bond to produce Ir-CHCH-PPh3 group and (ii) the activation of the ring-methyl group of the coordinated Cp* (C5Me5 −) to produce Ir(η5-C5Me4CH2-PPh3) group from reactions of iridium(III)-Cp* complexes, [Cp*IrL3]n+ (n=1, 2); Cp*=C5Me5 −; L3=Cl(PPh3)2 (3), (CH3CN)3 (5). The following new P-C bond containing iridium(III) complexes have been prepared: [Cp*Ir(-CHCH-PPh3)Cl(PPh3)]+ (4) from 3 with HCCH; [Ir(η5-C5Me4CH2-PPh3)(H)(PPh3)2]2+ (6) from 5 with PPh3; [Cp*Ir(-CHCH-PPh3)2(PPh3)]2+ (7) from 5 with HCCH and PPh3; [Ir(η5-C5Me4CH2-PPh3)(-CHCH-PPh3)Cl(PPh3)]2+ (8) from [Ir(η5-C5Me4CH2-PPh3)(Cl)(PPh3)2]2+ (6-Cl) with HCCH; [Ir(η5-C5Me3(1,3-CH2-PPh3)2(H)(PPh3)2)]3+ (10) from [Ir(η5-C5Me4CH2-PPh3)(NCCH3)2(PPh3)]3+ (9) with PPh3; [Ir(η5-C5Me4CH2-PPh3)(-CHCH-PPh3)2(PPh3)]3+ (11) from 9 with HCCH and PPh3.  相似文献   

7.
Heterocyclic thioamides, namely, imidazolidine-2-thione (imdzSH), 1-methyl-1, 3-imidazoline-2-thione (mimzSH), thiazolidine-2-thione (tzdSH) and 2,4-dithiouracil (dtucH2) with silver(I)/copper(I) salts in presence of triphenyl phosphine (PPh3) have yielded complexes of different nuclearity: mononuclear, [Ag(η1-S-HL)(PPh3)2Cl] (HL = imdzSH 1, mimzSH 2, tzdSH 3), dinuclear, [Ag21-S-tzdSH)2(μ-S-tzdSH)2(PPh3)2](NO3)24, and polynuclear, {Cu(μ-S,S-dtucH2)(PPh3)2X} (X = Cl 5, Br 6, I 7). All complexes have been characterized using analytical data, IR and multinuclear NMR spectroscopy (1H, 13C and 31P) and single crystal X-ray crystallography. The thio-ligands are bonded to the metal centers as neutral sulfur donors. The geometry around each metal center is distorted tetrahedral. Complexes 5-7 represent first examples of polymers of 2,4-dithiouracil in its coordination chemistry with metal salts. The hydrogen bonding interactions lead to the formation of 1D (2, 3, 7) and 2D (1, 4-6) sheet structures.  相似文献   

8.
A series of osmium(VI) nitrido complexes containing pyridine-carboxylato ligands OsVI(N)(L)2X (L = pyridine-2carboxylate (1), 2-quinaldinate (2) and X = Cl (a), Br (1b and 2c) or CH3O (2b)) and [OsVI(N)(L)X3] (L = pyridine-2,6-dicarboxylate (3) and X = Cl (a) or Br (b)) have been synthesised. Complexes 1 and 2 are electrophilic and react readily with various nucleophiles such as phosphine, sulfide and azide. Reaction of OsVI(N)(L)2X (1 and 2) with triphenylphosphine produces the osmium(IV) phosphiniminato complexes OsVI(NPPh3)(L)2X (4 and 5). The kinetics of nitrogen atom transfer from the complexes OsVI(N)(L)2Br (2c) (L = 2-quinaldinate) with triphenylphosphine have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law is obtained: −d[Os(VI)]/dt = k2[Os(VI)][PPh3]. OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) reacts also with [PPN](N3) to give an osmium(III) dichloro complex, trans-[PPN][OsIII(L)2Cl2] (6). Reaction of OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) with lithium sulfide produces an osmium(II) thionitrosyl complex OsII(NS)(L)2Cl (7). These complexes have been structurally characterised by X-ray crystallography.  相似文献   

9.
The new pyridine-based NNN tridentate ligand 2,6-C5H3N(CMe2NH2)2 (1) was synthesized by the treatment of 2,6-pyridinedicarbonitrile with an excess of the organocerium reagent in situ generated from CeCl3 and methyllithium in THF. The reaction of 1 with [RuCl2(PPh3)3] in THF at ambient conditions afforded (OC-6-23)-[RuCl{2,6-C5H3N(CMe2NH2)2}(PPh3)2]Cl (2). The corresponding dimethyl sulfoxide complex [RuCl{2,6-C5H3N(CMe2NH2)2}{S(O)Me2}2]Cl (3) was isolated as a mixture of the (OC-6-23) and (OC-6-32) stereoisomers 3a and 3b from the reaction between 1 and (OC-6-22)-[RuCl2{S(O)Me2}3(OSMe2)] in toluene at 80 °C. A prolonged interaction in toluene at reflux temperature gave isomerically pure 3a. The metal trichloride hydrates MCl3 · xH2O (M = Ru, Rh, Ir; x ≅ 2-4) produced mer-[RuCl3{2,6-C5H3N(CMe2NH2)2}] (M = Ru: 4; Rh: 5; Ir: 6), when combined with 1 in refluxing ethanol. The crystal structures of the following compounds were determined: ligand 1 and complexes 2-5 as addition compounds 2 · CH2Cl2, 3a · C7H8, 4 · EtOH and .  相似文献   

10.
The reaction of dimeric precursor [Ir(CO)2Cl]2 with two molar equivalent of the pyridine-ester ligands (L) like methyl picolinate (a), ethyl picolinate (b), methyl nicotinate (c), ethyl nicotinate (d), methyl isonicotinate (e) and ethyl isonicotinate (f) affords the tetra coordinated neutral complexes of the type [Ir(CO)2ClL] (1a-f). The single crystal X-ray structure of 1d reveals that the Ir atom occupies the centre of an approximately square planar geometry with two CO groups cis- to each other. Intermolecular C-H?O and Ir?C interactions greatly stabilize the supramolecular structure of 1d in the solid state. The oxidative addition (OA) reactions of 1a-f with different electrophiles such as CH3I, C2H5I and I2 undergo decarbonylation of one CO group to generate the oxidized products of the type [Ir(CO)RClIL] where R = -CH3 (2a-f); -C2H5 (3a-f) and [Ir(CO)ClI2L] (4a-f). Kinetic study of the reaction of 1c-f with CH3I indicates a first order reaction which follow the order 1d > 1c > 1f > 1e. All the synthesized complexes were characterized by elemental analyses, IR, and multinuclear NMR spectroscopy.  相似文献   

11.
In the presence of sodium nitrite, the reaction of methyl anthranilate and 2-aminopyridine or o-aminobenzoic acid gives two triazenes, 1-[(2-carboxymethyl)benzene]-3-[2-pyridine]triazene (HL) and 1-[(2-carboxymethyl)benzene]-3-[o-aminobenzoic acid]triazene (H2L′), respectively. In the presence of Et3N, the reaction of Pt(PPh3)2Cl2 and HL or H2L′ produces two triazenido platinum(II) complexes, Pt(PPh3)2(L)Cl (1) and Pt(PPh3)2(L′) (2), respectively, which have been characterized by X-ray crystallography, 31P NMR spectra, UV-Vis spectra, emission spectra and cyclic voltammetry. When excited at 310 nm, complexes 1 and 2 show luminescence at 432 and 442 nm, respectively, which is consistent with the trend of the lowest-energy absorption wavelengths of 1 (376 nm) and 2 (379 nm). Complexes 1 and 2 exhibit one or two redox waves and follow the order 1 (0.97 V) → 2 (0.89 and 0.07 V), which is also in accordance with the trend of the lowest-energy absorption spectra of 1 (376 nm) and 2 (379 nm).  相似文献   

12.
Six copper(I) complexes {[Cu2(L1)(PPh3)2I2] · 2CH2Cl2}n (1), {[Cu2(L2)(PPh3)2]BF4}n (2), [Cu2(L3)(PPh3)4I2] · 2CH2Cl2 (3), [Cu2(L4)(PPh3)4I2] (4), [Cu2(L5)(PPh3)2I2] (5) and [Cu2(L6)(PPh3)2I2] (6) have been prepared by reactions of bis(schiff base) ligands: pyridine-4-carbaldehyde azine (L1), 1,2-bis(4′-pyridylmethyleneamino)ethane (L2), pyridine-3-carbaldehyde azine (L3), 1,2-bis(3′-pyridylmethyleneamino)ethane (L4), pyridine-2-carbaldehyde azine (L5), 1,2-bis(2′-pyridylmethyleneamino)ethane (L6) with PPh3 and copper(I) salt, respectively. Ligand L1 or L2 links (PPh3)2Cu2(μ-I)2 units to form an infinite coordination polymer chain. Ligand 3 or 4 acts as a monodentate ligand to coordinate two copper(I) atoms yielding a dimer. Ligand 5 or 6 chelates two copper(I) atoms using pyridyl nitrogen and imine nitrogen to form a dimer. Complexes 1-4 exhibit photoluminescence in the solid state at room temperature. The emission has been attributed to be intraligand π-π* transition mixed with MLCT characters.  相似文献   

13.
The distorted square-planar complexes [Pd(PNHP)Cl]Cl (1) (PNHP = bis[2-(diphenylphosphino)ethyl]amine), [M(P3)Cl]Cl [P3 = bis[2-(diphenylphosphino)ethyl]phenylphosphine; M = Pd (2), Pt (3)] and [Pt(NP3)Cl]Cl (5) (NP3 = tris[2-(diphenylphosphino)ethyl]amine), coexisting in the later case with a square-pyramidal arrangement, react with one equivalent of CuCl to give the mononuclear heteroionic systems [M(L)Cl](CuCl2) [L = PNHP, M = Pd (1a); L = P3, M = Pd (2a), Pt (3a); L = NP3, M = Pt (5a)]. The crystal structure of 3a confirms that Pt(II) retains the distorted square-planar geometry of 3 in the cation with P3 acting as tridentate chelating ligand, the central P atom being trans to one chloride. The counter anion is a nearly linear dichlorocuprate(I) ion. However, the five-coordinate complexes [Pd(NP3)Cl]Cl (4), [M(PP3)Cl]Cl (M = Pd (6), Pt (7); PP3 = tris[2-(diphenylphosphino)ethyl] phosphine) containing three fused five-membered chelate rings undergo a ring-opening by interaction with one (4, 6, 7) and two (6, 7) equivalents of CuCl with formation of neutral MCu(L)Cl3 [L = NP3, M = Pd (4a); L = PP3, M = Pd (6a), Pt (7a)] and ionic [MCu(PP3)Cl2](CuCl2) [M = Pd (6b), Pt (7b)] compounds, respectively. The heteronuclear systems were shown by 31P NMR to have structures where the phosphines are acting as tridentate chelating ligands to M(II) and monodentate bridging to Cu(I). Further additions of CuCl to the neutral species 6a and 7a in a 1:1 ratio resulted in the achievement of the ionic complexes 6b and 7b with ions as counter anions. It was demonstrated that the formation of heterobimetallic or just mononuclear mixed salt complexes was clearly influenced by the polyphosphine arrangement with the tripodal ligands giving the former compounds. However, complexes [M(NP3)Cl]Cl constitute one exception and the type of reaction undergone versus CuCl is a function of the d8 metal centre.  相似文献   

14.
Thiocarbonate ruthenium complexes of the form CpRu(L)(L′)SCO2R (L = L′ = PPh3 (1), 1/2 dppe (2), L = PPh3, L′ = CO (3); R = Et (a), Bun (b), C6H5 (c), 4-C6H4NO2 (d)) have been synthesized by the reaction of the corresponding sulfhydryl complexes, CpRu(L)(L′)SH, with chloroformates, ROCOCl, at low temperature. The bis(triphenylphosphine) complexes 1 can be converted to 3 under CO atmosphere. The crystal structures of CpRu(PPh3)2SCO2Bun (1b), CpRu(dppe)SCO2Bun (2b), and CpRu(PPh3)(CO)SCO2Bun (3b) are reported.  相似文献   

15.
Schiff bases of 2-hydroxybenzophenone (HBP) (C6H5)(2-HOC6H4)CN(CH2)nEAr (L1/L2: E = S, Ar = Ph, n = 2/3; L3/L4: E = Se, Ar = Ph, n = 2/3; L5/L6: E = Te, Ar = 4-MeOC6H4, n = 2/3) and their complexes [PdCl(L-H)] (L = L1L6; 1, 2, 3, 5, 7, 11), [PtCl(L3-H/L5-H)] (4/8), [PtCl2(L4/L6)2] (6/12), [(p-cymene)RuCl(L5/L6)]Cl (9/13) and [HgBr2(L5/L6)2] (10/14) have been synthesized and characterized by proton, carbon-13, selenium-77 and tellurium-125 NMR, IR and mass spectra. Single crystal structures of L1, 1, 3, 4, 5 and 7 were solved. The Pd-E bond distances (Å): 2.2563(6) (E = S), 2.3575(6)−2.392(2) (E = Se); 2.5117(5)−2.5198(5) (E = Te) are near the lower end of the bond length range known for them. The Pt-Se bond length, 2.3470(8) Å, is also closer to the short values reported so far. The Heck and Suzuki reaction were carried out using complexes 1, 3, 5 and 7 as catalysts under aerobic condition. The percentage yields for trans product in Heck reaction were found upto 85%.  相似文献   

16.
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes.  相似文献   

17.
The Indox ligands, [{(S)-(iPr)Indox}n]H (1) [n=2 (a), 3 (b)] and [{(H)Indox}n=3]H (2), in which an indenyl group and an oxazoline ring are connected by an ethylene or propylene spacer, have been prepared. Reaction of [Ir(coe)2Cl]2 or [RhCl(C2H4)2]2 with the potassium salt of 1 afforded η5-[{(S)-(iPr)Indox}n]Ir(coe)2 (3) or η5-[{(S)-(iPr)Indox}n]Rh(C2H4)2 (6) as a 1:1 mixture of two diastereomers. The oxazoline ring in 3 and 6 did not coordinate to the metal center. When the complexes 3 or 6 reacted with iodine in diethyl ether, oxidative addition proceeded and the oxazoline ring coordinated to the metal center to give diiodoiridium(III) or rhodium(III) complexes, η51-[{(S)-(iPr)Indox}n]M(I)2 [M=Ir (4), Rh (7)]. The corresponding diiodoiridium(III) complex bearing the Indox ligand 2, η51-[{(H)Indox}n=2]Ir(I)2 (5), was also prepared by a similar method. Reaction of 4 or 7 with PPh3 in THF afforded diiodo-phosphine complexes, η5-[{(S)-(iPr)Indox}n]M(PPh3)(I)2 [M=Ir (8), Rh (9)] as a 1:1 mixture of two diastereomers in which the oxazoline ring dissociated from the metal center. The related reaction of 8 or 9 with more than 2 equiv. of AgOTf afforded the cationic complexes, [η51-[{(S)-(iPr)Indox}n]M(PPh3)(OTf)]OTf [M=Ir (10), Rh (11)], having a stereogenic center at the metal center as a mixture of only two diastereomers. From 1H and 31P NMR analyses, each diastereomer of 8 or 9 afforded only a single isomer of 10 or 11. The corresponding iridium(III) complex bearing the Indox ligand 2, [η51-[{(H)Indox}n=3]Ir(PPh3)(OTf)]OTf (12) was also prepared. The coordinated triflate ligand of 12 was slowly replaced by water in CDCl3 to afford the dicationic aquo complex, (S*pl,R*Ir)-[η51-[{(H)Indox}n=3]Ir(PPh3)(H2O)](OTf)2 (13). The monocationic complex, [η51-[{(S)-(iPr)Indox}n=2]Ir(PPh3)(I)]OTf (14a), having metal-centered chirality, was observed as a mixture of only two diastereomers in the reaction of 10a (a mixture of two diastereomers) with 1 equiv. of AgOTf. These observations indicated that the ligand exchange reaction of 8 or 9 with AgOTf contained the following three steps: (i) abstraction of one of the two prochiral iododes by AgOTf, (ii) recoordination of the oxazoline ring, and (iii) exchange of the remaining iodide for the triflate by AgOTf. The stereochemistry around the metal center was determined at the second step. All complexes have been characterized by usual spectroscopic methods as well as elemental analyses, and 4 and 13 have been characterized by X-ray analyses.  相似文献   

18.
Preparation and characterization of (triphenylphosphine)ruthenium complexes bearing N,O,N′-tridentate ligands, [(L1)RuCl(PPh3)2](BF4) (L1 = 2-[(2-pyridylmethoxy)methyl]pyridine), 1), [(L2)RuCl(PPh3)2](BF4) (L2 = 8-(2-pyridylmethoxy)quinoline, 2) and [(L3)RuCl2(PPh3)] (L3 = 2-[(2-pyridylmethoxy)methyl]quinoline, 3) are described. Complexes 1-3 have been characterized by NMR and elemental analyses. Molecular structures of 2 and 3 have been determined by X-ray crystallography. Both compounds exhibit the octahedral geometry. L2 adopts the facial configuration in 2 while L3 is in a mer-arrangement in 3. Complexes 1-3 have proven to be able to catalyze the transfer hydrogenation of several ketones to alcohols in the presence of KOH and 2-propanol at refluxing, among which complex 3 was found to be the most active.  相似文献   

19.
Cytidine (cyt) and adenosine (ado) react with cis-[L2Pt(μ-OH)]2(NO3)2 (L = PMe3, PPh3) in various solvents to give the nucleoside complexes cis-[L2Pt{cyt(− H),N3N4}]3(NO3)3 (L = PMe3, 1),cis-[L2Pt{cyt(− H),N4}(cyt,N3)]NO3 (L = PPh3, 2), cis-[L2Pt{ado(− H),N1N6}]2(NO3)2 (L = PMe3, 3) and cis-[L2Pt{ado(− H),N6N7}]NO3 (L = PPh3, 4). When the condensation reaction is carried out in solution of nitriles (RCN, R = Me, Ph) the amidine derivatives cis-[(PPh3)2PtNH=C(R){cyt(− 2H)}]NO3 (R = Me, 5a; R = Ph, 5b) and cis-[(PPh3)2PtNH=C(R){ado(− 2H)}]NO3 (R = Me, 6a: R = Ph, 6b) are quantitatively formed. The coordination mode of these nucleosides, characterized in solution by multinuclear NMR spectroscopy and mass spectrometry, is similar to that previously observed for the nucleobases 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd). The cytotoxic properties of the new complexes, and those of the nucleobase analogs, cis-[(PPh3)2PtNH=C(R){1-MeCy(− 2H)}]NO3 (R = Me, 7a: R = Ph, 7b), cis-[(PPh3)2PtNH=C(R){9-MeAd(− 2H)}]NO3 (R = Me, 8a: R = Ph, 8b) have been investigated in a wide panel of human cancer cells. Interestingly, whereas the Pt(II) nucleoside complexes (1-4) did not show appreciable cytotoxicity, the corresponding amidine derivatives (7a, 7b, 8a, 8b, 5b, and 6b) exhibited a significant in vitro antitumor activity.  相似文献   

20.
A metathesis reaction of [CpMCl2(PR3)] [M = Rh, R = Ph (1), Me (3); M = Ir, R = Ph (2), Me (4)] takes place in the presence of potassium butadienesulfinate (SO2CHCHCHCH2)K (9) to afford the mononuclear compounds [CpM(Cl)(PR3)(η1-SO2CHCHCHCH2)] [M = Rh, R = Ph (11S), (11W); M = Rh, R = Me (13S), (13W)] and [M = Ir, R = Ph (12S); M = Ir, R = Me (14S), (14W)] under different reaction conditions. The addition of PR3 (R = Ph, Me) to CpIr(Cl)[(1,2,5-η)-SO2CHCHCHCH2] (7) affords the corresponding iridium isomers 12S, 12W and 14S, in a non-selective reaction, along with the corresponding dichloride compounds 2 or 4. The 1H and 13C{1H} NMR data are consistent with the butadienesulfonyl ligands coordinated exclusively through the sulfur atom, and they show the presence of two isomers, described as the S and W conformers, which can be isolated separately. There is clear evidence that these isomers correspond to the kinetic and thermodynamic derivatives, respectively.  相似文献   

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