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1.
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
2.
Octahedral cis-Fe(CH3)2{2-(benzoyl)pyridyl-N,O}(PMe3)2 (1), square-pyramidal Co(CH3){2-(benzoyl)pyridyl-N,O}(PMe3)2 (2), and triangular-planar Ni{2-(benzoyl)pyridyl-η2-C,O}(PMe3)2 (3) have been synthesized by reaction of 2-benzoylpyridine with thermally labile Fe(CH3)2(PMe3)4 and Co(CH3)(PMe3)4 complexes. With Ni(CH3)2(PMe3)3, reductive elimination of ethane is observed when a η2-C,O-coordination is constituted. The complexes were investigated by NMR spectroscopic methods and the molecular structures of 1 and 2 were determined by X-ray crystallography. 相似文献
3.
Reaction between the binuclear hydroxo complex cis-[(PPh3)2Pt(μ-OH)]2X2 (X− = NO3, 1a; , 1b) and the model DNA base 9-methyladenine (9-MeAd) leads to the formation of the mononuclear species cis-[(PPh3)2Pt{9-MeAd(-H),N6N7}]X (X− = NO3, 2a; PF6, 2b), in which the nucleobase chelates the Pt(II) ion with the N6 and N7 atoms. The coordination mode of the nucleobase has been determinated through a multinuclear (1H, 31P, 13C, 15N and 195Pt) NMR analysis and the nuclearity of the complex has been obtained by E.S.I. mass spectrometry. 2 represents the first example of an isolated platinum complex in which the NH2-deprotonated adenine exhibits this binding mode. 相似文献
4.
Fabiola Estudiante-Negrete Simón Hernández-Ortega David Morales-Morales 《Inorganica chimica acta》2007,360(5):1651-1660
The organometallic tin(IV) complexes [SnPh2(SRF)2] SRF = −SC6F4-4-H (1), −SC6F5 (2), were synthesized and their reactivity with [MCl2(PPh3)2] M = Ni, Pd and Pt explored. Thus, transmetallation products were obtained affording polymeric [Ni(SRF)(μ-SRF)]n, monomeric cis-[Pt(PPh3)2(SC6F4-4-H)2] (3) and cis-[Pt(PPh3)2(SC6F5)2] (4) and dimeric species [Pd(PPh3)(SC6F4-4-H)(μ-SC6F4-4-H)]2 (5) and [Pd(PPh3)(SC6F5)(μ-SC6F5)]2 (6) for Ni, Pt and Pd, respectively. The crystal structures of complexes 1, 2, 3, 4 and 6 were determined. 相似文献
5.
cis,trans-Fe(CO)2(PMe3)2(p-Y-C6H4)X [X=Br, Y=H (4a), MeO (4b), Cl (4c), F (4d), Me (4e); X=I, Y=H (5); X=Cl, Y=H (6)] and cis,trans-Fe(CO)2(PMe3)2(σ-CHCH2)X [X=Br (7); X=I (8); X=Cl (9)] are prepared by reacting dihalide complexes cis,trans,cis- Fe(CO)2(PMe3)2X2 [X=Br (1), X=I (2), X=Cl (3)] with Grignard reagents p-Y-C6H4-MgBr (Y=H, OMe, Cl, F, Me) or CH2CH-MgBr and with lithium reagents PhLi, CH2CH-Li. With both reagents, the reaction proceeds following two parallel pathways: one is the metallation reaction which yields alkyl derivatives, the other affords 17 electron complexes [Fe(CO)2(PMe3)2X] via monoelectron reductive elimination. The influence of the halides and organometallic reagents on the yield of the metallation reaction is discussed. The solution structure of the complexes is assigned on the basis of IR and 1H, 13C, 19F, 31P NMR spectra. The solid state structure of complexes 4a, 5 and 6 is determined by single crystal X-ray diffractometric methods. 相似文献
6.
Egla Yareth Bivián-Castro 《Inorganica chimica acta》2005,358(7):2395-2402
The 1:1 and 1:2 complexes of cis-(NH3)2PtII with 9-methyladeninium cations, 9-MeAH+, have been prepared and characterized by X-ray crystallography: cis-[(NH3)2Pt(9-MeAH-N7)Cl](NO3)2 (1) and cis-[(NH3)2Pt(9-MeAH-N7)2](NO3)4 · 2HNO3 · 2H2O (2). The pKa values for 9-MeAH+ in H2O are 1.7 in 1 as well as 0.4 (pKa1) and 1.3 (pKa2) for 2, as determined by pD dependent 1H NMR spectroscopy. Compound 2 is special in that it crystallizes with two equivalents of HNO3 per Pt entity. The HNO3 molecules are stacked in rectangular channels provided by cis-(NH3)2PtII units, 9-methyladeninium ligands and nitrate anions, which form a porous network of hydrogen bonds. 相似文献
7.
Benjamin G. Harvey 《Inorganica chimica acta》2010,363(1):221-224
Refluxing WCl4(PMe3)3 under a nitrogen atmosphere in the presence of two equivalents of sodium amalgam leads to a reduction to the W(II) complex [cis,mer-WCl2(PMe3)3]2N2 (1), which can be converted to [mer,trans-WCl3(PMe3)2]2N2 (2) via appropriate oxidation/chlorination. Structural data have been obtained for both complexes, and demonstrate significantly increased steric crowding in 1 due to PMe3/PMe3 interactions. The N-N bond distances in the two compounds are similar, at 1.279(4) and 1.243(18) Å, respectively. 相似文献
8.
The “amidate-hanging” Pt mononuclear complexes, which can easily bind a second metal ion with the non-coordinated oxygen atoms in the amidate moieties, have been synthesized and characterized by 1H NMR, MS, IR spectroscopy, and single crystal X-ray analysis. Five new complexes with various amidate ligands and co-ligands, cis-[Pt(PVM)2(en)] · 4H2O (1, PVM = pivaloamidate, en = ethylenediamine), cis-[Pt(PVM)2(NH2CH3)2] · H2O (2), cis-[Pt(PVM)2(NH2tBu)2] (3), cis-[Pt(TCM)2(NH3)2] (4, TCM = trichloroacetamidate), and cis-[Pt(BZM)2(NH3)2] (5, BZM = benzamidate), were successfully synthesized by direct base hydrolysis of the corresponding Pt nitrile complexes, cis-[Pt(NCR)2(Am)2]2+ (P1, P2, P3, and P5) (NCR = nitrile, Am = amine). These nitrile complexes were obtained by introducing nitriles into the Pt aqua complexes, cis-[Pt(OH2)2(Am)2](ClO4)2, whereas introduction of trichloronitrile into [Pt(OH2)2(NH3)2](ClO4)2 induced more facilitated water nucleophilic attack to afford [Pt(TCM)(NH(COH)CCl3)(NH3)2](ClO4) (P4). The base treatments of the precursor complexes (P1-5) lead to produce “amidate-hanging” Pt mononuclear complexes (1-5) without geometry isomerization. The 195Pt chemical shifts for 1-5 exhibit subtle differences of the Pt electron densities among them. 相似文献
9.
Paul A. Humphrey Anthony F. Masters Leslie D. Field Mark G. Humphrey Inge Asselberghs Marek Samoc 《Inorganica chimica acta》2005,358(5):1663-1672
The complexes [Ru{(Z)-HCCHPh}(CO)2(η5-C5Ph5)] (1) and [Ru{(Z)-HCCHC6H4NO2}(CO)2(η5-C5Ph5)] (2) have been synthesized and their identity confirmed by single-crystal X-ray diffraction studies. Reaction of 2 with PMe2Ph and Me3NO in tetrahydrofuran afforded [Ru{(Z)-HCCHC6H4NO2}(CO)(PMe2Ph)(η5-C5Ph5)] (3). Cyclic voltammetry confirms the expected increase in ease of oxidation on proceeding from 2 to 1 and from 2 to 3. Hyper-Rayleigh scattering studies at 1064 nm reveal a dramatic increase in quadratic non-linearity on co-ligand replacement of CO by PMe2Ph, in proceeding from 2 to 3. Z-scan studies at 800 nm are consistent with significant contribution from two-photon states, and with an increase in γreal on co-ligand replacement of CO by PMe2Ph in proceeding from 2 to 3. 相似文献
10.
Gabriella Tamasi Agnese Magnani Luisa Chiasserini Chiara Gabbiani Michael A. Jakupec Michael B. Hursthouse 《Journal of inorganic biochemistry》2010,104(8):799-313
The reaction of aqueous cis-[Pt(NH3)2(H2O)2](NO3)2 with Na+HMEL− (H2MEL, meloxicam, 4-hydroxy-2-methyl-N-(5-methyl-1,3-thiazol-2-yl)-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide), and Na+HISO− (H2ISO, isoxicam, 4-hydroxy-2-methyl-N-(5-methylisoxazol-3-yl)-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide) at pH 7 produced micro-crystalline cis-[Pt(NH3)2(N1′-HMEL)2], 5 and cis-[Pt(NH3)2(N1′-HISO)2], 6. The X-ray diffraction structure of 5 shows two HMEL− anions donating through the thiazole nitrogen atoms and adopting a head-to-tail (HT) conformation. The 1H NMR spectrum for 5 from DMSO-d6 shows inertness of the complex up to at least 24 h. Delivery studies for 5 and 6 from vinyl hydrogel based on l-phenylalanine (pH 6.5, 25 °C) show that concentrations of complexes ranging between 2.5 and 5 μM can be reached after a day. Compounds 5 and 6 show strong anti-proliferative effects on CH1 cells (ovarian carcinoma, human) in vitro, IC50 values being 0.60 and 0.37 μM, respectively (0.16 μM for reference, cis-diamminodichloridoplatinum(II), cisplatin). ESI-MS measurements clearly documented that both 5 and 6 form adducts with the three model proteins ubiquitin (UBI), cytochrome c (CYT C) and superoxide dismutase (SOD), the HISO− complex being significantly more effective than the HMEL− one. Density functional methods help in finding rationale for the easiest dissociation of Pt-H2ISO/HISO bonds when compared to the Pt-N1′-H2MEL/N1′-HMEL linkages. 相似文献
11.
Palladium(II) and platinum(II) complexes with N-alkylpyridylpyrazole-derived ligands, 2-(1-ethyl-5-phenyl-1H-pyrazol-3-yl)pyridine (L1) and 2-(1-octyl-5-phenyl-1H-pyrazol-3-yl)pyridine (L2), cis-[MCl2(L)] (M = Pd(II), Pt(II)), have been synthesised. Treatment of [PdCl2(L)] (L = L1, L2) with excess of ligand (L1, L2), pyridine (py) or triphenylphosphine (PPh3) in the presence of AgBF4 and NaBPh4 produced the following complexes: [Pd(L)2](BPh4)2, [Pd(L)(py)2](BPh4)2 and [Pd(L)(PPh3)2](BPh4)2. All complexes have been characterised by elemental analyses, conductivity, IR and NMR spectroscopies. The crystal structures of cis-[PdCl2(L2)] (2) and cis-[PtCl2(L1)] (3) were determined by a single crystal X-ray diffraction method. In both complexes, the metal atom is coordinated by one pyrazole nitrogen, one pyridine nitrogen and two chlorine atoms in a distorted square-planar geometry. In complex 3, π-π stacking between pairs of molecules is observed. 相似文献
12.
Tobias Rüffer Björn Bräuer Bernhard Walfort Annie K. Powell Lorenzo Sorace 《Inorganica chimica acta》2007,360(12):3777-3784
The new mononuclear bis(oxamato) complex [n-Bu4N]2[Cu(obbo)] (1) (obbo=o-benzyl-bis(oxamato)) has been synthesized as a precursor for trinuclear oxamato-bridged transition metal complexes. Starting from 1 the homotrinuclear complexes [Cu3(obbo)(pmdta)2(NO3)](NO3)·CH2Cl2·H2O (2) and [Cu3(obbo)(tmeda)2(NO3)2(dmf)] (3) have been prepared, where pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine, tmeda = N,N,N′,N′-tetramethylethylenediamine and dmf = dimethylformamide. The crystal structures of 1-3 were solved. The magnetic properties of 2 and 3 were studied by susceptibility measurements versus temperature. For the intramolecular J parameter values of −111 cm−1 (2) and −363 cm−1 (3) were obtained. 相似文献
13.
Two new pyrazole-derived ligands, 1-ethyl-3,5-bis(2-pyridyl)pyrazole (L1) and 1-octyl-3,5-bis(2-pyridyl)pyrazole (L2), both containing alkyl groups at position 1 were prepared by reaction between 3,5-bis(2-pyridyl) pyrazole and the appropriate bromoalkane in toluene using sodium ethoxide as base.The reaction between L1, L2 and [MCl2(CH3CN)2] (M = Pd(II), Pt(II)) resulted in the formation complexes of formula [MCl2(L)] (M = Pd(II), L = L1 (1); M = Pd(II), L = L2 (2); M = Pt(II), L = L1 (3); M = Pt(II), L = L2 (4)). These complexes were characterised by elemental analyses, conductivity measurements, infrared, 1H, 13C{1H} NMR and HMQC spectroscopies. The X-ray structure of the complex [PtCl2(L2)] (4) was determined. In this complex, Npyridine and Npyrazole donor atoms coordinate the ligand to the metal, which complete its coordination with two chloro ligands in a cis disposition. 相似文献
14.
Reaction of platinum(II) salts with 5-ferrocenylpyrimidine (FcPM) afforded cis-[Pt(NH3)2(FcPM)2](PF6)2 (1), trans-[Pt(NH3)2(FcPM)2](PF6)2 (2), cis-[PtCl2(FcPM)2] (3), and cis-[PtCl2(DMSO)(FcPM)] (4): their spectroscopic and electrochemical properties were investigated. Complexes 1 and 2 were structurally characterized by X-ray crystallography. 相似文献
15.
The synthesis of a series of lanthanide tetracyanoplatinates containing the auxiliary ligands 1,10′-phenanthroline (phen) or 2,2′-bipyridine (bpy) have been carried out by reaction of Ln3+ nitrate salts with phen or bpy and potassium tetracyanoplatinate in solvent systems containing dimethylsulfoxide and dimethylformamide. The use of these solvents has lead to the isolation of [{Ln(DMSO)2(C12H8N2)(H2O)3}2Pt(CN)4](Pt(CN)4)2·2C12H8N2·4H2O (Ln = Eu (Eu-1), Tb (Tb-1), Yb(Yb-1)), [Ln(DMF)3(C12H8N2)(H2O)2NO3]Pt(CN)4 (Ln = La (La-2), Eu (Eu-2), Tb (Tb-2)), and [Ln(DMF)3(C10H8N2)(H2O)2NO3]Pt(CN)4 (Ln = La (La-3), Sm (Sm-3), Eu (Eu-3), Tb (Tb-3)) in the form of single crystals. Single-crystal X-ray diffraction has been used to investigate their structural features. The use of DMSO versus DMF as the solvent results in markedly different structural features. Eu-1 contains [{Eu(DMSO)2(C12H8N2)(H2O)3}2Pt(CN)4]2+ complex cations where the two Eu3+ centers are linked by a trans-bridging Pt(CN)42− anion to form a dimeric lanthanide complex cation. An additional uncoordinated Pt(CN)42− anion balances charge. Eu-2 and Eu-3 consist of zero-dimensional salts with [Eu(DMF)3(C12H8N2)(H2O)2(NO3)]2+ or [Eu(DMF)3(C10H8N2)(H2O)2(NO3)]2+ complex cations, respectively, and only non-coordinated Pt(CN)42− anions. Photoluminescence measurements illustrate that the Eu3+ and Tb3+ compounds for all three structure types display enhanced emission due to intramolecular energy transfer from the coordinated cyclic amines. 相似文献
16.
Ennio Zangrando 《Inorganica chimica acta》2009,362(3):820-60
The preparation and structural characterization of several new Ru(II) complexes in which four coordination positions are occupied by the sulfur atoms of a macrocycle, either 1,4,7,10-tetrathiacyclododecane ([12]aneS4) or 1,5,9,13-tetrathiacyclohexadecane ([16]aneS4), and the two others by relatively labile ligands (Cl−, , H2O, dmso-S), are described:cis-[Ru([12]aneS4)(dmso-S)(H2O)](CF3SO3)2 (2a), cis-[Ru([12]aneS4)(dmso-S)(ONO2)](NO3) (2b), cis-[Ru([16]aneS4)Cl2] (4), and trans-[Ru([16]aneS4)(dmso-S)(H2O)](CF3SO3)2 (5).The complexes of the larger [16]aneS4 macrocycle have a flexible coordination geometry, either cis or trans, that makes them unsuited for being used as precursors in metal-driven self-assembly processes.On the contrary, the [12]aneS4 complexes cis-[Ru([12]aneS4)(dmso-S)Cl]Cl (1) and, above all, its chlorido free derivatives cis-[Ru([12]aneS4)(dmso-S)(H2O)](CF3SO3)2 (2a) and cis-[Ru([12]aneS4)(dmso-S)(ONO2)](NO3) (2b) are potential precursors of the geometrically stable 90° bis-acceptor fragment cis-[Ru([12]aneS4)]2+.Preliminary results of their reactivity towards the linear linker pyrazine (pyz) showed that the nature of the isolated product depends on that of the counter-anion.When treated with pyz 2b afforded the dinuclear complex [{Ru([12]aneS4)(ONO2)}2(μ-pyz)](NO3)2 (8), while 2a gave the molecular triangle [{cis-Ru([12]aneS4)(μ-pyz)}3](CF3SO3)6 (9), both in low yields.The X-ray structures of compounds 2a, 2b, 4, 5, [{Ru([12]aneS4)Cl}2(μ-pyz)]Cl2 (7), 9, and of the sandwich complex[Ru([12]aneS3-S)2](CF3SO3)2 (3), in which only three sulfur atoms of each macrocycle are bound to ruthenium, are also described. 相似文献
17.
The phenyldi(2-thienyl)phosphine (PhPTh2) complexes [Os3(CO)12−n(PhPTh2)n] (n = 1-3) (1-3) have been prepared. Thermolysis of 1 and either 2 or 3 in octane affords carbon-hydrogen bond activation products [Os3(CO)9{μ3-PPhTh(C4H2S)}(μ-H)] (4) and [Os3(CO)8(PPhTh2){μ3-PPhTh(C4H2S)}(μ-H)] (5), respectively. Both exist as isomeric mixtures differing in the relative positions of phenyl and thienyl substituents with respect to the triosmium centre. The nature of the process has been confirmed by a single crystal X-ray diffraction analysis of 4. 相似文献
18.
Laura Battan Mario Manassero Alessandro Pasini Mirella Sansoni 《Inorganica chimica acta》2005,358(3):555-564
The interaction of an excess of the title ligands L− with the cis-Pt(phos)2 moieties gives compounds a-bcis-[Pt(L-O)2(phos)2] (a, phos = P(Ph)3; b, phos = 1/2 dppe), in which O- is preferred to S-coordination. Such preference is confirmed by the fact that the same products are obtained by reaction of excess of L− with the previously reported a-d complexes [Pt(L-O,S)(phos)2]+, (c, phos = PPh3, d, phos = 1/2 dppe), for which chelate ring opening occurs with rupture of Pt-S rather than Pt-O bonds. Compound a can be obtained also by oxidative addition of HL to [Pt(PPh3)3]. The Pt-O bonds in compounds a-d are stable towards substitution by Me2SO, pyridine and tetramethylthiourea. Substitution of L’s occurs with N,N′-diethyldithiocarbamate, which forms a very stable chelate with Pt(II). Thiourea and N,N′-dimethylthiourea also react, because they give rise to cyclometallated products [Pt(phos)2(NRC(S)NHR)]+ (R = H, CH3), with one ionised thioamido group, as revealed by an X-ray investigation of [Pt(PPh3)2(NHC(S)NH2)]+. The preference of O versus S coordination, as well as the stability of the Pt-O bonds, are discussed in terms of antisymbiosis. 相似文献
19.
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
20.
The reaction of trans(N)-[Co(d-pen)2]− (pen = penicillaminate) with HgCl2 or HgBr2 in the molar ratios of 1:1 gave the sulfur-bridged heterodinuclear complex, [HgX(OH2){Co(d-pen)2}] (X = Cl (1a) or Br (1b)). A similar reaction in the ratio of 2:1 produced the trinuclear complex, [Hg{Co(d-pen)2}2] (1c). The enantiomers of 1a and 1c, [HgCl(OH2){Co(l-pen)2}] (1a′) and [Hg{Co(l-pen)2}2] (1c′), were also obtained by using trans(N)-[Co(l-pen)2]− instead of trans(N)-[Co(d-pen)2]−. Further, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]− with HgCl2 in the molar ratio of 1:1 resulted in the formation of [HgCl(OH2){Co(d-pen)(l-pen)}] (2a). During the formations of the above six complexes, 1a, 1b, 1c, 1a′, 1c′, and 2a, the octahedral Co(III) units retain their configurations. On the other hand, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]− with HgCl2 in the molar ratio of 2:1 gave not [Hg{Co(d-pen)(l-pen}2] but [Hg{Co(d-pen)2}{Co(l-pen)2}] (2c), accompanied by the ligand-exchange on the terminal Co(III) units. The X-ray crystal structural analyses show that the central Hg(II) atom in 1c takes a considerably distorted tetrahedral geometry, whereas that in 2c is of an ideal tetrahedron. The interconversion between the complexes is also examined. The electronic absorption, CD, and NMR spectral behavior of the complexes is discussed in relation to the crystal structures of 1c and 2c. 相似文献