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1.
The preparations and spectroscopic characteristics are reported of a series of (trimethylgermyl)methyl- and (trimethylstannyl)methylplatinum(II) complexes with diene and P-donor ancillary ligands, cis-Pt(CH 2GeMe 3) 2L 2 (L = PPh 3 or PPh 2Me; L 2 = dppe or cod) and cis-Pt(CH 2SnMe 3) 2L 2 (L = PPh 3; L 2 =cod). Thermolysis of toluene solutions of cis-Pt(CH 2GeMe 3) 2(PPh 3) 2 leads to cis-Pt(Me)(CH 2GeMe 2CH 2GeMe 3)(PPh 3) 2 via β-alkyl migration, after (non-rate-limiting) phosphine dissociation. Estimated activation parameters (Δ H298 K‡ = 126 ± 3 kJ mol −1, Δ S‡ = + 17 ± 7 J mol −1 K −1 and hence Δ 298 K‡ = 121 ± 5 kJ mol −1) suggest that this system is more migration labile than its silicon analogue, primarily as a result of a lower activation enthalpy. While cis-Pt(CH 2GeMe 3) 2(PPh 2Me) 2 reacts similarly but less readily, Pt(CH 2GeMe 3) 2(dppe) 2 is inert at operable temperatures. Thermolysis of Pt(CH 2GeMe 3) 2(cod) generates 1,1,3,3,-tetramethyldi-1,3-germacyclobutane as the major organogermanium product, while from cis-Pt(CH 2SnMe 3) 2(PPh 3) 2, 1,1,3,3-tetramethyldi-1,3-stannacyclobutane predominates. Mechanistic implications are discussed. 相似文献
2.
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
3.
Reaction of cis-[Ptph 2(SMe 2) 2] with Me 2PCH 2PMe 2 (dmpm) gave cis-[PtPh 2(dmpm-P) 2] (1) or cis,cis-[Pt 2Ph 4(μ-dmpm) 2] (2) and reaction of 1 with [Pt 2Me 4(μ-SMe 2) 2] gave cis,cis-[Ph 2Pt(μ-dmpm) 2PtMe 2] (3). Reaction of 1 with trans-[PtClR(SMe 2) 2] gave cis, trans-[Ph 2Pt(μ-dmpm) 2PtClR], R = Me (5) or Ph (6), and in polar solvents, these isomerized to give [Ph 2Pt(μ-dmpm) 2PtR] +Cl −. When R = Me, further isomerization via the phenyl group transfer gave [PhMePt(μ-dmpm) 2PtPh] +Cl −. Oxidative addition of methyl iodide occurred reversibly at the cis-[PtMe 2P 2 unit of 3 to give cis, fac-[Ph 2Pt(μ-dmpm) 2PtIMe 3] but complex 2 failed to react with MeI. A comparison with similar known complexes of Ph 2PCH 2PPh 2 (dppm) is made and differences are attributed primarily to the lower steric hindrance of dmpm. 相似文献
4.
The reaction of K[H 6ReL 2] with [RuHCl(CO)(PPh 3) 3−x {P(OPr i} 3) x](L 2 = (PMePh 2) 2, dppe, (AsPh 3) 2, or (PPh 3) 2; x = 0, 1 or 2) leads to [L 2(CO)HRe(μ-H) 3RuH(PPh 3) 2−y{P(OPr i) 3} y] ( x = 0 or 1, Y = 0; X = 2, Y = 1(L 2 = PPh 3)) in a first step. Under the reaction conditions most of these complexes react rapidly with the liberated phosphine giving [L 2(CO)Re(μ-H) 3Ru(PPh 3) 3−y- {P(OPr i) 3} y] (L 2 = (PMePh 2) 2 or dppe, Y = 0; L 2 = (PPh 3) 2, Y = 1) as the only iso complexes. The structure of [(PMePh 2) 2(CO)Re(μ-H) 3Ru(PPh 3) 3] has been establishedby X-ray structure analysis. The complex [(PPh 3) 2(CO)Re(μ-H) 3Ru(PPh 3) 2(P(OPr i) 3)] reacts with molecular hydrogen under pressure to generate [L 2(CO)HRe(μ-H) 3RuH(PPh 3)(P(OPr i) 3) as the sole product. 相似文献
5.
Complexes trans-[PtX(L)(PPh 3) 2]A [1: X = CF 3; A = BF 4; L = NCNH 2, NCNMe 2, NCNEt 2, or NCNC(NH 2) 2. 2: X = Cl; A = BPh 4; L = NCNMe 2 or NCNEt 2] and cis-[PtCl(L)(PPh 3) 2][BPh 4] [3: L = NCNH 2 or NCNC(NH 2) 2], which appear to be the first cyanamide or cyanoguanidine complexes of platinum to be reported, have been prepared by treatment of trans-[PtBr(CF 3)(PPh 3) 2] (in CH 2Cl 2/acetone and in the presence of Ag[BF 4]) or of cis-[PtCl 2(PPh 3) 2] (in THF and in the presence of Na[BPh 4]), respectively, with the appropriate substrate. In KBr pellets or in solution 1 (L = NCNMe 2 or NCNEt 2) undergoes ready replacement of the organocyanamide (under the trans influence of CF 3) by bromide to regenerate trans-(PtBr(CF 3)(PPh 3) 2]. The X-ray structure of 1 (X = CF 3, A = BF 4, L = NCNEt 2) is also reported, and shows the presence of two apical intramolecular contacts of the metal with two ortho-hydrogen atoms of the phosphines, whereas the amine N atom of the diethylcyanamide is trigonal planar in the linear NCN framework with a delocalized π system. 相似文献
6.
The chiral bis-imine (1 R,2 R)-C 6H 10-[ E---N=CH---C 6H 3---3,4-(OMe) 2] 2 1 (LH) reacts with [Pd(OAc) 2] (1:1 molar ratio; OAc=acetate) giving the orthometallated [Pd(OAc)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)-C 6H 10--- N=CH---C 6H 3-3′,4′-(OMe) 2-κ-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-κ-C,N,N)]), through C---H bond activation on only one of the aryl rings and N, N-coordination of the two iminic N atoms. 2 reacts with an excess of LiCl to give [Pd(Cl)(L-κ-C,N,N)] 3. The reaction of 3 with AgClO 4 and neutral or anionic ligands L′ (1:1:1 molar ratio) affords [Pd(L-κ-C,N,N)(L′)](ClO 4) (L′=PPh 3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(I)(L-κ-C,N,N)] 8. Complex 4a reacts with wet CDCl 3 giving [Pd( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)(PPh 3)](ClO 4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b·CH 2Cl 2 has been determined by X-ray diffraction methods. Cleavage of the Pd---N bond trans to the C aryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac- O, O′)(L-κ-C,N)] 9 and [Pd(L-κ-C,N)(dppe-P,P′)](ClO 4) 12, while classical N, N′-chelating ligands such as 1,10-phenantroline (phen) or 2,2′-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-κ-C,N,N)(κ 1-N-phen)](ClO 4) 10 and [Pd(L-κ-C,N,N)(κ 1-N-bipy)](ClO 4) 11. Treatment of 1 with PtCl 2(DMSO) 2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl 2Pt[( NH 2) 2C 6H 10---N,N′] 13a and [Pt(Cl)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)] 13b, while [Pt(Cl)(L-κ-C,N,N)] 14 can be obtained by reaction of [Pt(μ-Cl)(η 3-2-Me---C 3H 4)] 2 with 1 in refluxing CHCl 3. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity. 相似文献
7.
Complexes of the types (a) trans- and cis-[Pd(C 6X 5) 2 (CNR) 2], (b) trans- [Pd(C 6X 5)Cl(CNR) 2] and (c) [Pd(C 6X 5)(CNR) 3]ClO 4 (X = F or Cl;R = Bu t cyclohexyl or p-tolyl) have been made by replacement of the tetrahydrothiophen or Cl groups of appropriate precursors by isonitrile. Their structures have been assigned on the basis of their IR and 1H NMR spectra. 相似文献
8.
The study of the reactivity of [Pt 2M 4(CCR) 8] (M=Ag or cu; R=Ph or tBu) towards different neutral and anionic ligands is reported. This study reveals that reactions of the phenylacetylide derivatives [Pt 2M 4(CCPh) 8] with anionic, X − (X=Cl or Br) or neutral donors (CN tBu or py) in a molar ratio 1:4 (m/donor ratio 1:1) yield the trinuclear anionic (NBu 4) 2[{Pt(CCPh) 4 (MX) 2] (M=Ag or Cu, X =Cl or Br) or neutral [{Pt(CCPh0 4=sAGL) 2] (L=CN tBu or py) complexes, respectively. The crystal structure of (NBu 4) 2[{Pt(CCPh) 4}(CuBr) 2](4) shows that the anion is formed by a dianionic Pt(CCPh) 4 fragment and two neutral CuBr units joined through bridging alkynyl ligands. All the alkynyl groups are σ bonded to Pt and η 2-coordinated to a Cu atom which have an approximately trigonal-planar geometry. By contrast, similar reactions with [Pt 2M 4(CC tBu) 8] (molar ratio M/donor 1:1) afford hexanuclear dianionic (NBu 4) 2[Pt 2M 4(CC tBu) 8X 2] or neutral [Pt 2Ag 4(CC tBu0 8Py 2]. Only by treatment with a large exces of Br − (molar ratio M/Br − 1:2) are the trinuclear complexes (NBu 4) 2[{Pt(CC tBu 4 (MBr) 2] (M=Ag, Cu) obtained. Attempted preparations of analogous complexes with phosphines (L′=PPh 3 or PEt 3) by reactions of [Pt 2M 4(CCR 8] with L′ leads to displacement of alkynyl ligands from platinum and formation of neutral mononuclear complexes [ trans-Pt(CCR) 2L′ 2]. 相似文献
9.
Reaction of Hg(S 7N) 2 with cis- PtCl 2(PR 3) 2 (PR 3 = PPh 3, PPh 2Me, PPHMe 2, PEt 3) in the presence of Na[PF 6] gives [Pt(S 3N)(PR 3) 2][PF 6] in 32–46% yield. The complexes have been characterized by IR, NMR and microanalyses. The X-ray crystal structures of two examples (PR 3 = PPh 2Me and PEt 3) show that the S 3N − ligand coordinates in a bidentate fashion via two sulphur atoms. 相似文献
10.
Mononuclear copper(II) complexes of a family of pyridylmethylamide ligands HL, HL Me, HL Ph, HL Me3 and HL Ph3, [HL = N-(2-pyridylmethyl)acetamide; HL Me = N-(2-pyridylmethyl)propionamide; HL Ph = 2-phenyl- N-(2-pyridylmethyl)acetamide; HL Me3 = 2,2-dimethyl- N-(2-pyridylmethyl)propionamide; HL Ph3 = 2,2,2-triphenyl- N-(2-pyridylmethyl)acetamide], were synthesized and characterized. The reaction of copper(II) salts with the pyridylmethylamide ligands yields complexes [Cu(HL) 2(OTf) 2] (1), [Cu(HL Me) 2](ClO 4) 2 (2), [Cu(HL) 2Cl] 2[CuCl 4] (3), [Cu(HL Me3) 2(THF)](OTf) 2 (4), [Cu(HL Me3) 2(H 2O)](ClO 4) 2 (5a and 5b), [Cu(HL Ph3) 2(H 2O)](ClO 4) 2 (6), [Cu(HL)(2,2′-bipy)(H 2O)](ClO 4) 2 (7), and [Cu(HL Ph)(2,2′-bipy)(H 2O)](ClO 4) 2 (8). All complexes were fully characterized, and the X-ray structures vary from four-coordinate square-planar, to five-coordinate square-pyramidal or trigonal-bipyramidal. The neutral ligands coordinate via the pyridyl N atom and carbonyl O atom in a bidentate fashion. The spectroscopic properties are typical of mononuclear copper(II) species with similar ligand sets, and are consistent their X-ray structures. 相似文献
11.
Isomerization of phenyl-substituted propargylplatinum(II) complex, trans-Pt(CH 2CCPh)(Cl)(PPh 3) 2 (1) to allenyl complex, trans-Pt(CPh=C=CH 2)(Cl)(PPh 3) 2 (2) was found to be catalyzed by zerovalent complex Pd(PPh 3) 4. The reaction was proposed to proceed through the transfer of the propargyl/allenyl ligand both from Pt(II) to Pd(0) and Pd(II) to Pt(0). The former transfer, which seemingly has a thermodynamic disadvantage, has unambiguously been confirmed to take place; treatment of 1 with Pd(PPh 3) 4 or a mixture of Pd 2(dba) 3 and PPh 3 resulted in the formation of Pd(I) complex, Pd 2(μ-PhCCCH 2)(μ-Cl)(PPh 3) 2 which lies in equilibrium with a mixture of propargyl/allenylpalladium(II) and Pd(0) complexes. 相似文献
12.
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
13.
In the reaction of cis-(CO) 4(SnPh 3)Re[C(OEt)NR 2] (R = ipr (isopropyl), chex (cyclohexyl)) with BI 3 the Lewis acid attacks the triphenylstannyl ligand. Substitution of a phenyl for a iodine group leads to equilibrium mixtures of rhenium carbene complexes of general formula cis-(CO) 4(SnPh 3−χI χ)Re[C(OEt)NR 2] (χ = 1−3; R = ipr, chex). By changing the solvent and ratio of can be shifted such that only one major product is formed. Thus this reaction pathway can be used for the preparation of cis-(CO) 4(SnPhI 2)Re[C(OEt)NR 2] (R = ipr, chex). Even when a large excess of BI 3 is present electrophilic attack by the Lewis acid on the carbene ligand is not observed. Synthesis of cis-(CO)4(SnPh3−χIχ)Re[C(OEt)NR2] (χ = 1−3; R --- ipr, chex) can be achieved in high yield by reaction of cis-(CO)4(SnPh3)Re[C(OEt)NR2] (R = ipr, chex) with one, two or three equivalents of HI. This reaction, with successive rupture of the tin-carbon bonds in the triphenylstannyl ligand and the simultaneous formation of benzene, affords the desired substitution product irreversibly. Reaction of cis-(CO)4(SnPh3)Re[C(OEt)NR2] (R = ipr, chex) with I2 gives the compounds, cis-(CO)4(SnI3)Re[C(OEt)NR2] (R = ipr, chex), in relatively low yields. 相似文献
14.
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
15.
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
16.
The ruthenium(II) complex [RuI 2(Me 2SO) 4] was synthesized and characterized. The Me 2SO ligands are all S-bonded. Reactions of RuI 2(Me 2SO) 4 with ligands containing P, N and S donor atoms have been carried out and the complexes obtained were characterized using different physical methods. [RuI 2L 4] (L= CH 3CN, Me 2SO and py), [RuI 2(CH 3CN) 2(PPh 3) 2] and [RuI 2(CS)(PPh 3) 3] have been synthesized using RuI 3 as the source material and characterized as above. 相似文献
17.
Reaction of trans-[ReCl(CNR)(dppe) 2] (R = Me (Ia) or tBu (Ib); DPPE = Ph 2PCH 2CH 2PPh 2) in CH 2Cl 2 with cynamide in the presence of TlBF 4 forms the new cynamide-isocyanide complexes trans-[Re(CNR)(NCNH 2)(dppe) 2][BF 4] (R = Me (IIa) or tBu (IIb)), which upon treatment by tBuOK or Et 3N give trans-[Re(NCNH)(CNR)(dppe) 2] (R = Me (IIIa) or tBu (IIIb)). The electrochemical behaviour of these species was studied by cyclic voltammetry and controlled potential electrolysis at a Pt electrode in an aprotic solvent, and cathodic reduction of II results in the formation of III. 相似文献
18.
Ruthenium(II) perchlorate complexes, [Ru(dppm) 3(ClO 4)]ClO 4 1, [Ru(dppe) 3(ClO 4)]ClO 4 2, and [Ru(dpae) 3(ClO 4)]ClO 4 3, catalyse the selective homogeneous oxidation of alkenes with TBHP and H 2O 2 as oxidizing agents. Oxidation of cyclohexene with TBHP gave 2-cyclohexene-1-ol, 2-cyclohexenone and 1-( tert-butylperoxy)-2-cyclohexene. The homogeneous liquid phase oxidation of cyclohexene with TBHP shows appreciable solvent effect. Styrene on oxidation with TBHP gave benzaldehyde as the major product and styrene oxide as the minor product. Oxidation with H 2O 2 is radical-initiated and gives low conversion to products. TBHP and H 2O 2 are compared for their oxidizing ability and TBHP is more effective than H 2O 2 as an oxidizing agent. Linear and long chain alkenes are not efficiently oxidized. Cyclooctene and trans-stilbene are oxidized to the corresponding epoxides. 相似文献
19.
Two mononuclear Ru II complexes of polypyridyl ligands, cis-[Ru(bpy) 2(4,4′-bpy)Cl](PF 6)·H 2O (1) and cis-[Ru(phen) 2(CH 3CN) 2](PF 6) 2 (2) (bpy=2,2′-bipyridyl, 4,4′-bpy=4,4′-bipyridyl, and PHEN=1,10-phenanthroline), have been synthesized and characterized by elemental analyses, IR and UV–vis spectra. The crystal structures of both complexes have been determined by X-ray diffraction, indicating that each Ru II center is hexa-coordinated (RuN 5Cl for 1 and RuN 6 for 2) and takes a distorted octahedral geometry. The favored feature of both complexes is that they are quite useful complex precursors for further constructing new functional architectures. 相似文献
20.
Reactions among Cu(ClO 4) 2 · 6H 2O, Cu(acac) 2/VO(acac) 2 and 3-methoxysalicylaldehyde Picoloylhydrazone in different solvents give three complexes, [Cu 2L(acac)(H 2O) 2]ClO 4 (1), [Cu 4L 2(acac) 2(py) 2](ClO 4) 2 (2) and (VO 2) 2L 2Cu 2(acac) 2 (3) (acac = acetyl acetonate and py = pyridine). There is an extended 2D structure in complex 1 constructed by hydrogen bonds between the binuclear complex cation and the ClO 4− anion, and an extended 1D structure in complex 2 constructed by weak ππ stacking interactions between neighboring cyclic tetranuclear complex molecules. Complex 3 is the first oxovanadium–copper complex with a bridging oxo oxygen atom between the V atom and the Cu atom. The solid-state photoluminescent properties of the three title complexes have been studied. There is an antiferromagnetic interaction in 1. 相似文献
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