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Vol．31No．12201012CHEMICALJOURNALOFCHINESEUNIVERSITIES2431～2437-··11231．2．3．510006PBE1PBECPCM-··．PtHOClPtPt5dCl3pH—OOPtPt—Cl．PtOPt—Cl．、63.6～386.3kJ/mol17.1～36.2kJ/mol．1B2B79.787.8kJ/mol、．trans-PtCl2i-pra2．O641A0251-0790201012-2431-072010-05-20．91510631010000372010B090400184．．E-mailxuxuan@scnu．edu．cn2070·Ⅱ1A1．2～4DNA56．、、、、78、、．Carboplatin1BOxaliplatin1C9．．Fig．1Structuresofcis-PtⅡandtrans-PtⅡcomplexestrans-Platin1Dtrans-PtCl2NH3210．．Farrell11～14PtⅡCl2LL'LL'NH3、、N-、．Montero1516、．17．Reishus3cis-PtCl2NH32+H2Ok1k幑幐－1cis-PtClNH32H2O++Cl－cis-PtClNH32H2O++H2Ok2k幑幐－2cis-PtNH32H2O22++Cl－deAlmeida18．Russo1920B3LYPCarboplatinOxaliplatin．Zhou21B3LYP1Etrans-PtCl2i-pradimatrans-PtCl2i-prapra．Francisco13-··trans-PtⅡCl2i-prahmpi-pra=iso-propylaminehmp=3-hydroxylmethyl-pyridine1F．1trans-PtⅡCl2i-prahmpPBE1PBE22B3LYP23、、、Pt6-31GdPtStuttgart-DresdenSDDαs=0.0075αp=0.013αd=0.025αf=0.980424MWB-60．CPCM25．ZPVE．IRC26．SDD6-311++G3df3pd298.15KΔH0—298l．Gaussian03．2PBE1PBEB3LYP1．12PtPt90°Cl1—Pt—N1—Cl2179.25°179.11°．Pt—ClPBE1PBEPt—Cl1Pt—Cl20.23290.2323nmB3LYP0.23620.2356nm0.23040.2294nm．PBE1PBEB3LYP．PBE1PBE201.06kJ/mol．PtCl1—Pt—N1—Cl2113.83°Pt3.82°～6.21°Pt—Cl1Pt—Cl20.24580.2467nm0.01530.0173nm．Table1Optimizedbondlengthsnmandbondangles°oftrans-PtⅡCl2i-prahmpMethodPt—N1Pt—N2Pt—Cl1Pt—Cl2N2—Pt—Cl1Cl1—Pt—N1N1—Pt—Cl2Cl2—Pt—N2Cl1—Pt—N1—Cl2Expt．120．20680．20270．23040．229489．7789．8790．3190．05179．84B3LYP0．20730．20420．23620．235691．5388．6387．8891．96179．11PBE1PBE0．20500．20180．23290．232391．5988．4088．0191．98179．250．2104*0．2076*0．2458*0．2467*95．48*86．33*86．18*96．21*113．83**Thebondlengthsandbondanglesintripletoftrans-PtⅡCl2i-prahmp．2342Vol．31PBE1PBE/SDD+6-31Gd．2．12．1．1RPt2Cl2NC1—N1—Pt—Cl2110.37°C2—N2—Pt—Cl246.78°．4Cl18．RCl2P11ACl2P11BCl1P21CCl1P21D．4P1Cl1P32AP1Cl1P32BP2Cl2P32CP2Cl2P32D．2、．Fig．2Optimizedstructuresofthefirstandsecondhydrolysisoftrans-PtⅡCl2i-prahmpBondlengthsareinnmandbondanglesindegree．．1A1B1C1D41I-XI-1I-2I-3I-42TS1-XTS1-1TS1-2TS1-3TS1-43I-X'I-1'I-2'I-3'I-4'4P1P2．4155i150i156i157icm－1．2A2B2C2D4．174i175i175i176icm－1．Pt—ClPt—OIRC．Pt—OPt—Cl3PtOPt—OPt—ClPt—Cl．2．1．2NBO1E21ClNHHO．RH2OHOClPtHOClPt．2NBOE21B3342No．12-··Fig．3Pt—OandPt—ClbondlengthsforthefirstAandsecondBhydrolysisprocessoftrans-PtⅡCl2i-prahmpTable2SecondorderperturbationstabilizationenergiesE2oftrans-PtⅡCl2i-prahmp…H2Ointeractionsofpaths1Band1CaPath1BDonorNBOsAcceptorNBOs*E2/kJ·mol－1Path1CDonorNBOs*AcceptorNBOs*E2/kJ·mol－1I-2LP3PtBD*1H—Ow133．15I-3LP3Cl1BD*1H—Ow133．44LP4PtBD*1H—Ow11．21LP4Cl1BD*1H—Ow12．01BD1H—Ow1LP*5Pt2．63LP1Cl1BD*1H—Ow11．17LP3Cl2BD*1H—Ow12．80LP2Ow1LP*5Pt0．75LP1Cl2LP*5Pt15．68LP4Cl1BD*1Pt—Cl2658．14LP4Cl2LP*5Pt208．37LP4Cl1LP*5Pt193．74TS1-2LP3Cl2BD*1H—Ow142．13TS1-3LP3Cl1BD*1H—Ow149．70LP4Cl2BD*1H—Ow118．48LP4Cl1BD*1H—Ow124．83LP1Cl2BD*1H—Ow13．55LP1Cl1BD*1H—Ow14．81LP2Ow1BD*1Pt—Cl195．22LP2Ow1BD*1Pt—Cl284．90LP2Ow1LP*5Pt25．33LP2Ow1LP*5Pt25．75LP4Cl2BD*1Pt—Cl1111．65LP4Cl1BD*1Pt—Cl2110．44LP4Cl2LP*5Pt51．41LP4Cl1LP*5Pt54．67I-2'LP4Cl2BD*1H—Ow1221．87I-3'LP4Cl1LP*1Hw1321．06LP1Cl2BD*1H—Ow115．72LP1Cl1LP*1Hw115．26LP2Ow1BD*1Pt—Cl1393．42LP2Ow1BD*1Pt—Cl2392．67LP1Ow1BD*1Pt—Cl122．32LP2Ow1LP*5Pt67．34a．LPdenoteslone-pairLP*denotesanti-lone-pairorbitalBDdenotesbondingorbitalBD*denotesanti-bondingorbital．I-2Pt5dH—Oσ*E234.36kJ/molHPt0.2359nmOPt0.3319nm．HCl2Cl23pH—Oσ*E22.80kJ/mol．3I-1I-3I-4H2OH—OClClH0.23950.24120.2384nm1CI-3LPCl1→σ*H—O36.62kJ/molPt—Cl1OPtFig．4Structureoftransitionstateofthefirsthydrolysisprocess．O、2ClPtN—Pt—NPt21．OHPtCl4Cl—Pt—O—Hw14°．N1—Pt—Ow184°～95°Cl1—Pt—N1—Cl2．TS1-1TS1-2TS1-3TS1-4H2OHCl0.21500.21330.21710.2129nmOPt0.24390.23960.24380.2420nm．TS1-22Cl23pH—OE264.16kJ/molLPO→LP*PtLPO→σ*Pt—Cl1E225.3395.22kJ/mol．O4342Vol．31PtHCl2．Pt—Cl2LPCl2→σ*PtE2I-2224.05kJ/molTS1-251.41kJ/mol．I-1'I-2'I-3'I-4'Cl—H0.18350.19060.19090.1844nmOPt0.20630.20790.20740.2062nm．1BI-2'LPCl2→σ*H—OE2237.59kJ/molLPO→σ*Pt—Cl1E2415.74kJ/mol．PtCl2．2B1B1C．2．2CPCMPBE1PBE/SDD+6-311++G3df3pdEtolaqZPVEEtol+ZPVEaqEtolg．3、ΔH0—298aq、ΔG0—298aq、ΔGsolv、HthermalS0—．Table3Relativeenergiesingas-phaseandaqueousrelativesolvationenergiesthermalcontributionstoen-thalpiesstandardentropiesrelativeenthalpiesandGibbsfreeenergiesat298.15Kforallinterme-diatespeciesISandtransitionstatesTSofthefirstandthesecondaquationprocessesPathStateΔEtolaq/kJ·mol－1ΔEtolg/kJ·mol－1ΔEtol+ZPVEaq/kJ·mol－1ΔGsolv/kJ·mol－1Hthermal/kJ·mol－1S0—0K/J·K－1·mol－1ΔH0—298aq/kJ·mol－1ΔG0—298aq/kJ·mol－11AI-1000－66．5780．5685．800TS1-190．7115．090．8－90．9777．6666．187．893．7I-1'38．4101．740．5－129．8778．9668．236．942．11BI-2000－67．7780．7701．700TS1-282．6112．283．2－97．3777．8653．179．794．2I-2'19．543．123．7－91．3781．0651．919．734．51CI-3000－64．1780．4699．100TS1-389．1106．291．2－81．2778．4653．187．1100．9I-3'15．450．520．5－99．2780．8649．815．830．51DI-4000－63．6778．6654．400TS1-482．8114．583．4－95．3778．0650．682．183．2I-4'28．482．630．7－117．8779．5656．129．328．62AI-5000－267．9844．6688．700TS2-1101．8121．9103．6－288．0842．5655．299．7109．7I-5'30．186．534．2－324．3843．8650．629．340．82BI-6000－279．0841．6646．400TS2-288．5124．788．3－315．2841．7656．588．685．5I-6'20．9115．423．5－373．5840．9627．220．225．92CI-7000－303．1843．971000TS2-3107．2128．6109．6