Lasri Jamal, Adília Januário Charmier M, da Silva M Fátima C Guedes, Pombeiro Armando J L
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisboa, Portugal.
Dalton Trans. 2007 Aug 14(30):3259-66. doi: 10.1039/b704329e. Epub 2007 Jun 1.
Iminoacylation of acetone oxime Me(2)C[double bond, length as m-dash]NOH upon reaction with trans-[PtCl(2)(NCCH(2)CO(2)Me)(2)] and [2 + 3] cycloaddition of acyclic nitrone (-)O(+)N(Me) = C(H)(C(6)H(4)Me-4) to a nitrile ligand in lead to the formation of mono-imine trans-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] [imine-a = NH[double bond, length as m-dash]C(CH(2)CO(2)Me)ON = CMe(2)] and mono-oxadiazoline trans-[PtCl(2)(oxadiazoline-a)(NCCH(2)CO(2)Me)] [oxadiazoline-a = [upper bond 1 start]N[double bond, length as m-dash]C(CH(2)CO(2)Me)ON(Me)Cupper bond 1 end(C(6)H(4)Me-4)] unsymmetric mixed ligand complexes, respectively, as the main products. Reactions of or with acetone oxime , cyclic nitrone (-)O(+)N = CHCH(2)CH(2)C[upper bond 1 end]Me(2) or N,N-diethylhydroxylamine give access, in moderate to good yields, to the unsymmetric mixed ligand oxadiazoline and/or imine complexes trans-[PtCl(2)(oxadiazoline-a)(imine-a)] , trans-[PtCl(2)(oxadiazoline-a)(oxadiazoline-b)] [oxadiazoline-b = [upper bond 1 start]N[double bond, length as m-dash]C(CH(2)CO(2)Me)O[lower bond 1 start]NCupper bond 1 endCH(2)CH(2)C[lower bond 1 end]Me(2)], trans-[PtCl(2)(imine-a)(imine-b)] [imine-b = NH = C(CH(2)CO(2)Me)ONEt(2)] or trans-[PtCl(2)(imine-a)(oxadiazoline-b)] . The cis mono-imine mixed ligand complex cis-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] is the major product from the reaction of cis-[PtCl(2)(NCCH(2)CO(2)Me)(2)] with the oxime , while the di-imine compound cis-[PtCl(2)(imine-a)(2)] is a minor product. Reaction of cis-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] with N,N-diethylhydroxylamine or the cyclic nitrone affords, in good yields, the unsymmetric mixed ligand complexes cis-[PtCl(2)(imine-a)(imine-b)] or cis-[PtCl(2)(imine-a)(oxadiazoline-b)] , respectively. All these complexes were characterized by elemental analyses, IR and (1)H, (13)C and (195)Pt NMR spectroscopies, and FAB(+)-MS. The X-ray structural analysis of trans-[PtCl(2){NH=C(CH(2)CO(2)Me)ON=CMe(2)}(NCCH(2)CO(2)Me)] is also reported.
丙酮肟Me(2)C[双键，键长为中横线]NOH与反式-[PtCl(2)(NCCH(2)CO(2)Me)(2)]反应时发生亚氨基酰化反应，以及无环硝酮(-)O(+)N(Me)=C(H)(C(6)H(4)Me-4)与腈配体发生[2 + 3]环加成反应，分别生成单亚胺反式-[PtCl(2)(亚胺-a)(NCCH(2)CO(2)Me)] [亚胺-a = NH[双键，键长为中横线]C(CH(2)CO(2)Me)ON = CMe(2)]和单恶二唑啉反式-[PtCl(2)(恶二唑啉-a)(NCCH(2)CO(2)Me)] [恶二唑啉-a = [上键1起始]N[双键，键长为中横线]C(CH(2)CO(2)Me)ON(Me)C上键1结束(C(6)H(4)Me-4)]不对称混合配体配合物作为主要产物。丙酮肟、环硝酮(-)O(+)N = CHCH(2)CH(2)C[上键1结束]Me(2)或N,N-二乙羟胺的反应，以中等至良好的产率得到不对称混合配体恶二唑啉和/或亚胺配合物反式-[PtCl(2)(恶二唑啉-a)(亚胺-a)]、反式-[PtCl(2)(恶二唑啉-a)(恶二唑啉-b)] [恶二唑啉-b = [上键1起始]N[双键，键长为中横线]C(CH(2)CO(2)Me)O[下键1起始]NC上键1结束CH(2)CH(2)C[下键1结束]Me(2)]、反式-[PtCl(2)(亚胺-a)(亚胺-b)] [亚胺-b = NH = C(CH(2)CO(2)Me)ONEt(2)]或反式-[PtCl(2)(亚胺-a)(恶二唑啉-b)]。顺式单亚胺混合配体配合物顺式-[PtCl(2)(亚胺-a)(NCCH(2)CO(2)Me)]是顺式-[PtCl(2)(NCCH(2)CO(2)Me)(2)]与肟反应的主要产物，而二亚胺化合物顺式-[PtCl(2)(亚胺-a)(2)]是次要产物。顺式-[PtCl(2)(亚胺-a)(NCCH(2)CO(2)Me)]与N,N-二乙羟胺或环硝酮反应，分别以良好的产率得到不对称混合配体配合物顺式-[PtCl(2)(亚胺-a)(亚胺-b)]或顺式-[PtCl(2)(亚胺-a)(恶二唑啉-b)]。所有这些配合物均通过元素分析、红外光谱以及(1)H、(13)C和(195)Pt核磁共振光谱和FAB(+)-质谱进行了表征。还报道了反式-[PtCl(2){NH=C(CH(2)CO(2)Me)ON=CMe(2)}(NCCH(2)CO(2)Me)]的X射线结构分析。
