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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Multinuclear platinum(II)-amine complexes containing bis(aniinopropyl)dicarba-closo-dodecaborane(12)ligands
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Multinuclear platinum(II)-amine complexes containing bis(aniinopropyl)dicarba-closo-dodecaborane(12)ligands

机译:含有双(苯胺基丙基)双氨基-闭-十二烷基硼烷(12)配体的多核铂(2)-氨基配合物

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摘要

Treatment of the bridging bidentate l,Z-bis(aminopropyl)-l,Z-dicarba-closo-dodecaborane(12)(1,Z-bis(aminopropyl)-l,Z-carborane)ligands of the type l,Z-{H_2N(CH_2)_3}_2-l,Z-C_2B_(10)H_(10)(L~1,Z = 7,5)or(L_2,Z = 12,6)with two equivalents of trans-[PtCl_2(NH_3)]~,followed by halogen ligand metathesis with AgOTf and HCl~(aq)afforded the novel diplatinum(II)-amine species cis-[{PtCl_2(NH_3)}_2L~n](7(n = 1)or 8(n-2),respectively).Similarly,the reaction of L~1 or L_2 with the labile trans-[PtCl(dmf)(NH_3)_2]~+ afforded trans-[{PtCl(NH_3)_2}_2L~n](OTf)_2(9(n-1)or 10(n= 2),respectively)in good yield and purity.However,isolation of the analogous 1,2-carborane complexes was not possible owing to decomposition reactions that led to extensive degradation of the carborane cage and reduction of the metal centre.The mixed dinuclear complex[cis-{PtCl_2(NH_3)}-L~1-trans-{PtCl(NH_3)_2}]OTf(19)was prepared by treatment of the Boc-protected amine ligand l-{(Boc)_2N(CH_2)_3}-7-{H_2N(CH_2)_3}-l,7-C_2B_(10)H_(10)(L~3,15)with trans-[PtCl(dml)(NH_3)_2]~+ to yield trans-[PtC!(NH_3)_2L~3]OTf(16),followed by acid deprotection of the pendant amine group,complexation with transs-[PtClI_2(NH_3)]~,and halogen ligand metathesis using AgOTf and HCl_(aq).A novel trinuclear species containing 5 was prepared by the addition of two equivalents of 15 to the labile precursor cis-[Pt(dmf)_2(NH_3)_2]_~(2+)followed by acid deprotection of the pendant amine groups.Further complexation with two equivalents of trans-[PtCH_2(NH_3)]~ followed by halogen ligand metathesis using AgOTf and HCl_(aq)afforded the triplatinum(II)-amine species[cis-{Pt(NH_3)_2(L1)_2}-cis-{PtCl_2(NH_3)}_2](OTf)_2(23).Complexes 7-10,19 and 23 represent the first examples of multinuclear platimim(II)-amine derivatives containing carborane cages.Preliminary in vitro cytotoxicity studies for selected complexes are also reported.
机译:处理桥接类型为L,Z-的双齿1,Z-双(氨基丙基)-1,Z-二氨基-氯代十二硼烷(12)(1,Z-双(氨基丙基)-1,Z-碳烷)配体{H_2N(CH_2)_3} _2-1,Z-C_2B_(10)H_(10)(L〜1,Z = 7,5)或(L_2,Z = 12,6)具有两个当量的反式[PtCl_2 (NH_3)]〜,然后进行卤素配位体与AgOTf和HCl〜(aq)的置换,得到了新型双铂(II)-胺类顺式[[{PtCl_2(NH_3)} _ 2L〜n](7(n = 1)或类似地,L〜1或L_2与不稳定的反式-[PtCl(dmf)(NH_3)_2]〜+的反应得到反式-[{PtCl(NH_3)_2} _2L〜 n](OTf)_2(9(n-1)或10(n = 2),分别具有良好的收率和纯度。但是,由于分解反应导致无法进行类似的1,2-碳戊烷络合物的分离通过处理制备了混合双核配合物[顺式-{PtCl_2(NH_3)}-L〜1-反式-{PtCl(NH_3)_2}] OTf(19)。 Boc保护的胺配体1-{(Boc)_2N(CH_2)_3} -7- {H_2N(CH_2)_3} -1,7-C_2B_(10)H的合成_(10)(L〜3,15)与反式[PtCl(dml)(NH_3)_2]〜+合成反式[PtC!(NH_3)_2L〜3] OTf(16)侧基胺基,与反式-[PtClI_2(NH_3)]〜络合,并使用AgOTf和HCl_(aq)进行卤素配位体复分解。通过向不稳定的前体顺式中加两个15的等价物,制得一个含有5个新的三核物质。 -[Pt(dmf)_2(NH_3)_2] _〜(2+),然后对侧链胺基进行酸脱保护。与两当量的反式-[PtCH_2(NH_3)]〜进一步络合,然后使用AgOTf进行卤素配位体复分解和HCl_(aq)负担了三铂(II)-胺类的[顺式-{Pt(NH_3)_2(L1)_2}-顺式-{PtCl_2(NH_3)} _ 2](OTf)_2(23)。络合物7- 10,19和23代表含有碳硼烷笼的多核铂亚胺(II)-胺衍生物的第一个实例。还报道了对某些复合物的初步体外细胞毒性研究。

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