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1.
1,2,4-Trimethyl-cyclohexadiene reacts with RuCl3 · nH2O in refluxing ethanol to afford quantitatively [RuCl2(1,2,4-C6H3Me3)]2 (1), the coordination of 1,2,4-trimethylbenzene to the ruthenium atom introducing planar chirality at the η6-arene ligand. The dinuclear complex 1 reacts with two equivalents of triphenylphosphine (PPh3) to give quantitatively, as a racemic mixture of enantiomers, [RuCl2(1,2,4-C6H3Me3)(PPh3)] (2), the structure of which has been determined by a single-crystal X-ray structure analysis of (rac)-2. Similarly, 1 reacts with two equivalents of the enantiopure phosphine (1S,2S,5R)-(+)-neomenthyldiphenylphosphine (nmdpp) to afford in good yield [RuCl2(1,2,4-C6H3Me3)(nmdpp)] (3) as a mixture of diastereoisomers, from which the isomer 3a was isolated by crystallisation. A single-crystal X-ray structure analysis of 3a allowed the determination of the absolute configuration at the planar chiral η6-arene moiety. Finally, complex 1 reacts with one equivalent of the diphosphine ligand 1,1′-bis(diphenylphosphino)ferrocene (dppfc) to give the heteronuclear complex [RuCl2(1,2,4-C6H3Me3) (dppfc)RuCl2(1,2,4-C6H3Me3)] (4). All complexes were fully characterised by elemental analysis, mass spectrometry, NMR and IR spectroscopies. 相似文献
2.
F. Nipa Haque 《Inorganica chimica acta》2008,361(11):3149-3158
The complexes RuHCl{PPh2(2-C6H4)CHNCH2CH2CH2NCH(2-C6H4)PPh2} (RuHCl{prP2N2}, 7) and RuHCl{PPh2(2-C6H4)CH2NHCH2CH2CH2NHCH2(2-C6H4)PPh2} (RuHCl{prP2(NH)2}, 8) are prepared by reaction of RuHCl(PPh3)3 with a ligand derived from 1,3-diaminopropane and ortho-diphenylphosphinobenzaldehyde. They are active precatalysts for the hydrogenation of acetophenone and are moderately active for the hydrogenation of benzonitrile and imines. The related complex RuHCl{ethP2(NH)2} with a ligand derived from 1,2-diaminoethane provides a more active catalyst. Complexes 7 and 8 undergo an unusual base-promoted isomerization reaction that produces a ruthenium complex containing a novel β-diiminato ligand. 相似文献
3.
Treatment of ‘RuCl3 · 3H2O’ with Ph2AsCH2AsPh2 (dpam) in hot EtOH gives either trans-[RuCl2(dpam-As,As′)(dpam-As)2] (1), or cis-[RuCl2(dpam-As,As′)2] (2), depending on the mole ratio. On exposure to light, solutions of 2 isomerise to trans-[RuCl2(dpam-As,As′)2] (3). Treatment of [RuCl2(PPh3)3] with two equivalents of dpam in CH2Cl2 gave a mixture of two products, from which trans-[RuCl2(PPh3) (dpam-As,As′)(dpam-As)] (4) was isolated by recrystallisation. The crystal structures of 1-4 are reported. Complexes 1-3 in CH2Cl2 undergo electrochemical oxidation to Ru(III), and the Ru(III) form of 2 undergoes isomerisation on the voltammetric timescale to the Ru(III) form of 3. 相似文献
4.
Lutz Dahlenburg Harald Treffert Jörg Dannhäuser Frank W. Heinemann 《Inorganica chimica acta》2007,360(5):1474-1481
The new pyridine-based N∩N∩N 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
5.
Mien Wei Lum 《Inorganica chimica acta》2004,357(3):769-774
Reactions of the clusters Os3(μ-H)2(μ3-1-OC10H6)(CO)9, 1, and Os3(μ-H)(μ-2-OC10H7)(CO)10, 2, with the group 15 ligands EPh3 (E=P, As, Sb) generally afforded the mono- and, or disubstituted derivatives. These derivatives tend to decompose during chromatographic separations on silica gel; thus one of the decomposition products from the reaction of 1 with PPh3 has been identified as Os(H)2(CO)2(PPh3)2, 3. The molecular structures of 3, as well as the derivatives Os3(μ-H)2(μ3-1-OC10H6)(CO)8(AsPh3), 4, Os3(μ-H)2(μ3-1-OC10H6)(CO)7(SbPh3)2, 5c, Os3(μ-H)(μ-2-OC10H7)(CO)8(AsPh3)2, 7b, and Os3(μ-H)(μ-2-OC10H7)(CO)8(SbPh3)2, 7c, have been determined by single crystal X-ray diffraction studies. 相似文献
6.
The reactions of [ReCl2{η2-NNC(O)Ph}(PPh3)2] (1) with t-BuOOH, in C6H6 or chlorinated solvents, at room temperature or with MeOH upon reflux in air lead to the trichloro-η1-benzoyldiazenido [ReCl3{η1-NNC(O)Ph}(PPh3)2] (2) or the methoxy-oxo [ReOCl2(OMe)(PPh3)2] (3) compound, respectively, which have been characterized by spectroscopic and FAB+-MS methods, elemental and single crystal X-ray diffraction analyses. They show distorted octahedral coordinaiton geometries with trans triphenylphosphine ligands, an essentially linear η1-diazenido moiety in 2 and the methoxy group in 3 in trans position to the oxo ligand. 相似文献
7.
Reaction of the potassium salts of (EtO)2P(O)CH2C6H4-4-(NHC(S)NHP(S)(OiPr)2) (HLI), (CH2NHC(S)NHP(S)(OiPr)2)2 (H2LII) or cyclam(C(S)NHP(S)(OiPr)2)4 (H4LIII) with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(CH2)1-3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to [Cu(PPh3)LI] (1), [Cu2(Ph2PCH2PPh2)2LII] (2), [Cu{Ph2P(CH2)2PPh2}LI] (3), [Cu{Ph2P(CH2)3PPh2}LI] (4), [Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (5), [Cu2(PPh3)2LII] (6), [Cu2(Ph2PCH2PPh2)LII] (7), [Cu2{Ph2P(CH2)2PPh2}2LII] (8), [Cu2{Ph2P(CH2)3PPh2}2LII] (9), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (10), [Cu8(Ph2PCH2PPh2)8LIIII4] (11), [Cu4{Ph2P(CH2)2PPh2}4LIII] (12), [Cu4{Ph2P(CH2)3PPh2}4LIII] (13) or [Cu4{Ph2P(C5H4FeC5H4)PPh2}4LIII] (14) complexes. The structures of these compounds were investigated by IR, 1H, 31P{1H} NMR spectroscopy; their compositions were examined by microanalysis. The luminescent properties of the complexes 1-14 in the solid state are reported. 相似文献
8.
The reaction of the racemic chiral methyl complex (η5-C5H5)Re(NO)(PPh3)(CH3) (1) with CF3SO3H and then NH2CH2C6H5 gives [(η5-C5H5)Re(NO)(PPh3)(NH2CH2C6H5)]+ ([4a-H]+; 73%), and deprotonation with t-BuOK affords the amido complex (η5-C5H5)Re(NO)(PPh3)(NHCH2C6H5) (76%). Reactions of 1 with Ph3C+ X− and then primary or secondary amines give [(η5-C5H5)Re(NO)(PPh3)(CH2NHRR′)]+ X− ([6-H]+ X−; R/R′/X = a, H/NH2CH2C6H5/BF4; a′, H/NH2CH2C6H5/PF6; b, H/NH2CH2(CH2)2CH3/PF6; c, H/(S)-NH2CH(CH3)C6H5/BF4); d, CH2CH3/CH2CH3/PF6; e, CH2(CH2)2CH3/CH2(CH2)2CH3/PF6; f, CH2C6H5/CH2C6H5/PF6; g, -CH2(CH2)2CH2-/PF6; h, -CH2(CH2)3CH2-/PF6; i, CH3/CH2CH2OH/PF6 (62-99%). Deprotonations with t-BuOK afford the amines (η5-C5H5)Re(NO)(PPh3)(CH2NRR′) (6a-i; 99-40%), which are more stable and isolated in analytically pure form when R ≠ H. Enantiopure 1 is used to prepare (RReSC)-[6c-H]+, (RReSC)-6c, (S)-[6g-H]+, and (S)-6g. The crystal structures of [4a-H]+, a previously prepared NH2CH2Si(CH3)3 analog, [6a′,d,f,h-H]+, (RReSC)-6c, and 6f are determined and analyzed in detail, particularly with respect to cation/anion hydrogen bonding and conformation. In contrast to analogous rhenium containing phosphines, 6a-i show poor activities in reactions that are catalyzed by organic amines. 相似文献
9.
Valerio BertolasiAndrea Marchi Lorenza MarvelliRoberto Rossi Claudio Bianchini Isaac de los RiosMaurizio Peruzzini 《Inorganica chimica acta》2002,327(1):140-146
The reaction of the rhenium(V) nitrido complex [Re(N)Cl2(PPh3)2] with the tripodal ligand N(CH2CH2PPh2)3 (NP3) in THF gave [Re(N)Cl2(η2-P,P-NP3)] (1) in which NP3 acts as a tridentate ligand using the nitrogen and two phosphorus donors for coordination. Refluxing 1 in a polar solvent such as ethanol produced [(η4-NP3)Re(N)Cl]Cl (2) in which NP3 acts as a tetradentate ligand. Treatment of complex [Re(O)Cl3(AsPh3)2] containing the [ReO]3+ core with NP3 in THF yielded [ReCl3{η3-N,P,P-(N{CH2CH2Ph2}2{CH2CH2P(O)Ph2})}] (3). Complexes 1 and 3 have been characterized by single-crystal X-ray analyses. 相似文献
10.
Using a phosphorus based Mannich condensation reaction the new pyridylphosphines {5-Ph2PCH2N(H)}C5H3(2-Cl)N (1-Cl) and {2-Ph2PCH2N(H)}C5H3(5-Br)N (1-Br) have been synthesised in good yields (60% and 88%, respectively) from Ph2PCH2OH and the appropriate aminopyridine. The ligands 1-Cl and 1-Br display variable coordination modes depending on the choice of late transition-metal complex used. Hence P-monodentate coordination has been observed for the mononuclear complexes AuCl(1-Cl) (2), AuCl(1-Br) (3), RuCl2(p-cymene)(1-Cl) (4), RuCl2(p-cymene)(1-Br) (5), RhCl2(Cp∗)(1-Cl) (6), RhCl2(Cp∗)(1-Br) (7), IrCl2(Cp∗)(1-Cl) (8), IrCl2(Cp∗)(1′-Cl) (8′), IrCl2(Cp∗)(1-Br) (9), cis-/trans-PdCl2(1-Cl)2 (10), cis-/trans-PdCl2(1-Br)2 (11), cis-PtCl2(1-Cl)2 (12) and cis-PtCl2(1-Br)2 (13). Reaction of Pd(Me)Cl(cod) (cod = cycloocta-1,5-diene) with either 1 equiv. of 1-Br or the known pyridylphosphines 1′-Cl, 1-OH or 1-H gave the P/N-chelate complexes Pd(Me)Cl(1-Br-1-H) (14)-(17). All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 4, 5, 10 and 16 · (CH3)2SO have been elucidated by single crystal X-ray crystallography. A crystal structure of the dinuclear metallocycle trans,trans-[PdCl2{μ-P/N-{Ph2PCH2N(H)}C5H4N}]2 · CHCl3, 18 · CHCl3, has also been determined. Here 1-H bridges, using both P and pyridyl N donors, two dichloropalladium centres affording a 12-membered ring with the PdCl2 units adopting a head-to-tail arrangement. 相似文献
11.
Two novel phosphino-phosphaferrocenes [η5-C5H4(CH2)nPPh2]Fe(η5-PC4H2-2,5-Cy2) (PP1: n=1; PP2: n=2) have been designed and prepared in order to clarify weak chelate effect in the previously reported (η5-C5H4CH2PPh2)Fe[η5-PC4H2-2,5-((-)-menthyl)2] (1). 31P NMR studies of reactions of PP1 with PdCl2(cod) (6) revealed that PP1 showed stronger tendency to coordinate to the PdII center in bidentate fashion compared to 1. On the other hand, chelate effect in PP2 was negligibly weak and a reaction of PP2 with 6 in a PP2/6 = 2/1 molar ratio gave a complex PdCl2(PP2)2 (10) cleanly in which PP2 coordinated to the palladium center at the PPh2 moiety as a monodentate ligand. X-ray crystal structure studies of chelate complexes PdCl2(PP1) (7) and PdCl2(PP2) (9) showed that 9 had deviations from an idealized geometry in the square planar complex which could be attributed to a larger chelate ring of PP2, while PP1 in 7 constructed nearly ideal geometry for the square planar complex.From comparison of the coordination behavior between 1, PP1, and PP2, it is concluded that steric bulk of (-)-menthyl groups in 1 is the main factor of the weak chelate coordination of 1. 相似文献
12.
The closo- and nido-carborane-diphenylphosphine complexes [Hg2{1,2-(PPh2)2-1,2-C2B10H10}2(μ-Cl2)2(μ-HgCl2)3]·2CH2Cl2 (1) and [HgCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] (2) have been synthesized and characterized by elemental analysis, FT-IR and X-ray structure determination. The X-ray structure analysis for these two complexes showed that the carborane cage ligand was coordinated bidentately to the Hg(II) center through its two phosphorus atoms. The coordination geometry of the mercury atom complexed by P2Cl2 unit in complex 1 or P3Cl unit in complex 2 was a distorted tetrahedron, while the mercury atom in complex 2 coordinated to six Cl atoms was a slightly distorted octahedron. X-ray analysis reveals that the complex 1 forms a 1D chain coordination polymer via bridged Hg-Cl bonds. For complex 2, it displays a 3D network constructed by the C-H···Cl hydrogen bonds and C-H···H-B dihydrogen bonds. 相似文献
13.
Heating a benzene solution of the isomerized product of spiro[4.4]nona-1,3-diene(dicarbonyl)[ethoxy(aryl)carbene]iron phosphine adduct [(η3-C9H12)Fe{C(OC2H5)(C6H4CH3-o)}(CO)2PPh3] (1) in a sealed quartz tube at 85-90 °C for 72 h gave the ring-opened η4 olefin-coordinated dicarbonyliron phosphine complex [Fe{η4-C5H7CHCHCH2CHC(OC2H5)C6H4CH3-o}(CO)2PPh3] (3) and cyclobutane derivative [C24H22O7] (4). The thermal decomposition of analogous isomerized product [(η3-C9H12)Fe{C(OC2H5)(C6H4CH3-p)}-(CO)2PPh3] (2) afforded the corresponding η4 olefin-coordinated dicarbonyliron phosphine complex [Fe{η4-C5H7CHCHCH2CHC(OC2H5)C6H4CH3-p}(CO)2PPh3] (6) and compound 4. The structures of products 3 and 4 have been established by X-ray diffraction studies. 相似文献
14.
Michael Gras 《Inorganica chimica acta》2011,371(1):59-62
The thermal reaction of Ru3(CO)12 with various carboxylic acids (benzoic, 4-hydroxyphenylacetic, ferrocenic, stearic, oleic, 4-(octadecyloxy)benzoic) in refluxing tetrahydrofuran, followed by addition of 5-(4-pyridyl)-10,15,20-triphenylporphyrin (L), gives the dinuclear complexes Ru2(CO)4(OOCR)2L2 (1: R = -C6H5, 2: R = -CH2-p-C6H4OH, 3: R = -C5H4FeC5H5, 4: R = -(CH2)16CH3, 5: R = -(CH2)7CHCH(CH2)7CH3, 6: R = -p-C6H4O(CH2)17CH3). Complexes 1-6 were characterised by IR, NMR, and ESI-MS as well as by elemental analysis. The UV-Vis spectra show the Soret band centred at 417 nm and the Q bands at 515, 550, 590 and 645 nm, respectively. 相似文献
15.
Chong Shik Chin 《Inorganica chimica acta》2004,357(10):3064-3070
Phosphorus-carbon bond is formed via: (i) the apparent HCCH insertion into Ir-P bond to produce Ir-CHCH-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(-CHCH-PPh3)Cl(PPh3)]+ (4) from 3 with HCCH; [Ir(η5-C5Me4CH2-PPh3)(H)(PPh3)2]2+ (6) from 5 with PPh3; [Cp*Ir(-CHCH-PPh3)2(PPh3)]2+ (7) from 5 with HCCH and PPh3; [Ir(η5-C5Me4CH2-PPh3)(-CHCH-PPh3)Cl(PPh3)]2+ (8) from [Ir(η5-C5Me4CH2-PPh3)(Cl)(PPh3)2]2+ (6-Cl) with HCCH; [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)(-CHCH-PPh3)2(PPh3)]3+ (11) from 9 with HCCH and PPh3. 相似文献
16.
Saponification of the bis(carbamic acid ester) 1,3-C6H4(CMe2NHCO2Me)2 (1), made by the addition of methanol to commercial 1,3-C6H4(CMe2NCO)2, yielded the meta-phenylene-based bis(tertiary carbinamine) 1,3-C6H4(CMe2NH2)2 (2). Dinuclear [{(η4-1,5-C8H12)RhCl}2{μ-1,3-C6H4(CMe2NH2)2}] (3) resulted from the action of 2 on [{(η4-1,5-C8H12)Rh(μ-Cl)}2] in toluene. Combination of 2 with PdCl2 or K2[PdCl4] gave the dipalladium macrocycle trans,trans-[{μ-1,3-C6H4(CMe2NH2)2}2(PdCl2)2] (4) along with cyclometalated [{2,6-C6H3(CMe2NH2)2-κN,κC1,κN′}PdCl] (5). Substitution of PEt3 for the labile chlorido ligand of 5 afforded [{2,6-C6H3(CMe2NH2)2-κN,κC1, κN′}Pd(PEt3)]Cl (6). The crystal structures of the following compounds were determined: bis(carbamic acid ester) 1, ligand 2 as its bis(trifluoroacetate) salt [1,3-C6H4(CMe2NH3)2](O2CCF3)2, 2 · (HAcf)2, complexes 3 and 6, as well as 1,3-C6H4(CMe2OH)2 (the diol analogue of 2). 相似文献
17.
The 2-methallyl complex [(η5-C9H7)Ru(η3-2-MeC3H4)(PPh3)] (3), prepared from [(η5-C9H7)Ru(PPh3)2Cl] (2) and 2-MeC3H4MgCl, reacts with HX (X = Cl, CF3CO2) in the presence of ethene to give the chiral-at-metal compounds [(η5-C9H7)Ru(C2H4)(PPh3)X] (4, 5) in nearly quantitative yields. Treatment of 2 with AgPF6 and ethene affords [(η5-C9H7)Ru(C2H4)(PPh3)2]PF6 (6), which reacts with acetone to give the substitution product [(η5-C9H7)Ru(OCMe2)(PPh3)2]PF6 (7). The molecular structure of 7 has been determined crystallographically. Whereas treatment of 4 with CH(CO2Et)N2 yields the olefin complex [(η5-C9H7)Ru{η2-(Z)-C2H2(CO2Et)2}(PPh3)Cl] (8), the reactions of 4 and 5 with Ph2CN2, PhCHN2 and (Me3Si)CHN2 lead to the formation of the carbeneruthenium(II) derivatives [(η5-C9H7)Ru(CRR′)(PPh3)Cl] (9-11) and [(η5-C9H7)Ru(CRR′)(PPh3)(κ1-O2CCF3)] (12-14), respectively. Treatment of 9 (R = R′ = Ph), 10 (R = H, R′ = Ph) and 11 (R = H, R′ = SiMe3) with MeLi produces the hydrido(olefin) complexes [(η5-C9H7)RuH(η2-CH2CPh2)(PPh3)] (15), [(η5-C9H7)RuH(η2-CH2CHPh)(PPh3)] (18a,b) and [(η5-C9H7)RuH(η2-CH2CHSiMe3)(PPh3)] (19) via C-C coupling and β-hydride shift. The analogous reactions of 11 with PhLi gives the η3-benzyl compound [(η5-C9H7)Ru{η3-(Me3Si)CHC6H5}(PPh3)] (20). The η3-allyl complex [(η5-C9H7)Ru(η3-1-PhC3H4)(PPh3)] (17) was prepared from 10 and CH2CHMgBr by nucleophilic attack. 相似文献
18.
Interactions between guanidinium cations and the sulfonate groups on the phosphine [PPh2C6H4-m-SO3]− have been exploited to incorporate iridium(I) centres into hydrogen-bonded networks. The crystal structure of [C(NH2)3]2{trans-[IrCl(CO)(PPh2C6H4-m-SO3)2]} (4) contains hexagonal guanidinium sulfonate (GS) sheets in which both of the sulfonate groups from each complex anion form hydrogen bonds within the same sheet. The crystal structures of [C(NH2)2(NHMe)][PPh2C6H4-m-SO3] (5) and [C(NH2)2(NHEt)][PPh2C6H4-m-SO3] (6) reveal that the GS sheets can tolerate the loss of one hydrogen bond donor, though twisting occurs to accommodate the alkyl group. However, the crystal structure of [C(NH2)2(NMe2)][PPh2C6H4-m-SO3] (7) shows that ribbon structures are formed instead of sheets when two hydrogen bond donors are lost. The compound [C(NH2)2(NHMe)]2{trans-[IrCl(CO)(PPh2C6H4-m-SO3)2]} · 3/8H2O (8) contains hydrogen-bonded cylinders as opposed to sheets. This is a likely consequence of a mismatch between the intramolecular S?S distance present in the anion, and the closer S?S distance present in a twisted GS sheet such as that in 5. The crystal structures of [C(NH2)2(NHEt)][P(O)Ph2C6H4-m-SO3] (9) and [C(NH2)2(NMe2)][P(O)Ph2C6H4-m-SO3] · H2O (10) show that the phosphine oxide group successfully competes with the sulfonate as a hydrogen bond acceptor. The crystal structure of 9 contains hydrogen-bonded ribbons that are interlinked through the anions which act as pillars to form a layer structure. In contrast, the crystal structure of 10 contains hydrogen-bonded sheets that involve cations, sulfonate groups, phosphine oxides and the included water molecule. These sheets are linked into a three-dimensional network through the anion pillars. 相似文献
19.
The reactions of a self-assembled silver(I) coordination polymer, [Ag2{μ-PriN(PPh2)2}(μ-NO3)2]n (1) with various bidentate N-donor ligands such as DABCO, 2,2′-bipyridyl and 1,10-phenanthroline yield 1-D helices or π-π stacked polymers, depending on the chelate vector of the N-donor ligand. The molecular structures of the resultant complexes, [Ag2{μ-PriN(PPh2)2}(DABCO)(NO3)2]n (2), [Ag2{μ-PriN(PPh2)2}(2,2′-bipy)2(NO3)2] (3) and [Ag2{μ-PriN(PPh2)2}(1,10-phen)2](NO3)2 (4) have been confirmed by single-crystal X-ray diffraction. Complex 2 exists as an infinite helical polymer because of the exo-bidentate nature of DABCO. Complex 3 assumes a 2D grid motif as a result of intermolecular π-π stacking among adjacent bipyridine moieties. The phenanthroline complex 4 exhibits strong inter- and intramolecular π-π stacking interactions. 相似文献
20.
Syntheses of three new N-arylanilido-arylimine bidentate Schiff base type ligand precursors, ortho-C6H4[NH(2,6-iPr2C6H3)](CHNAr1) [Ar1 = p-FC6H4 (2a); C6H5 (2b); p-OMeC6H4 (2c)], and their four-coordinated boron complexes, ortho-C6H4[N(2,6-iPr2C6H3)](CHNAr1)BF2 [Ar1 = p-FC6H4 (3a); C6H5 (3b); p-OMeC6H4 (3c)] are described. The boron complexes 3a-3c were synthesized from the reaction of BF3(OEt2) with the lithium salt of their corresponding ligand. All complexes were characterized by 1H and 13C NMR spectroscopy and molecular structures of complexes 3a and 3c were determined by X-ray crystallography. The photophysical properties of complexes 3a-3c were briefly examined. All three complexes display bright green fluorescence in solution and in the solid state. Electroluminescent devices with complex 3c as the emitter were fabricated. These devices were found to give green emission with maximum current efficiency of 2.92 cd/A and maximum luminance of 670 cd/m2. 相似文献