Investigating pyridazine and phthalazine exchange in a series of iridium complexes in order to define their role in the catalytic transfer of magnetisation from para-hydrogen.
Investigating pyridazine and phthalazine exchange in a series of iridium complexes in order to define their role in the catalytic transfer of magnetisation from para-hydrogen.
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DOI：
10.1039/c5sc00756a
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发表时间：
2015-07-01
期刊：
影响因子：
8.4
通讯作者：
Duckett SB
中科院分区：
文献类型：
--
作者：
Appleby KM;Mewis RE;Olaru AM;Green GGR;Fairlamb IJS;Duckett SB
[Ir（IMes）（COD）Cl]与哒嗪（pdz）或酞嗪（phth）和H2反应，生成仲氢磁化转移催化剂[Ir（H）2（IMes）（pdz）3]Cl和[Ir（H）2（IMes）（phth）3]Cl。[Ir（IMes）（COD）Cl]、[IMes = 1，3-双（2，4，6-三甲基苯基）咪唑-2-亚基，COD = 1，5-环辛烯]与哒嗪（pdz）和酞嗪（phth）反应生成[Ir（COD）（IMes）（pdz）]Cl和[Ir（COD）（IMes）（phth）]Cl。这两种配合物的核磁共振（NMR）研究表明，进行haptotropic位移，交换对结合配体内的质子。当这些络合物暴露于氢时，它们反应分别形成[Ir（H）2（COD）（IMes）（pdz）]Cl和[Ir（H）2（COD）（IMes）（phth）]Cl，其最终转化为[Ir（H）2（IMes）（pdz）3]Cl和[Ir（H）2（IMes）（phth）3]Cl，因为COD被氢化形成环辛烷。这两个二氢化物配合物示出，通过NMR，经历两个完整的N-杂环解离和haptotropic移位，其速率受空间相互作用和自由配体pKa值。使用这些配合物作为催化剂的转移极化从仲氢哒嗪和酞嗪通过可逆交换（SABRE）的信号放大进行了探索。未来可能使用的药物，其中包含哒嗪和酞嗪基序作为体内或临床磁共振成像探针的证明;一系列的NMR和幻影为基础的MRI测量报告。
Reaction of [Ir(IMes)(COD)Cl] with pyridazine (pdz) or phthalazine (phth) and H2 results in the formation of the para-hydrogen magnetisation transfer catalysts [Ir(H)2(IMes)(pdz)3]Cl and [Ir(H)2(IMes)(phth)3]Cl. The reaction of [Ir(IMes)(COD)Cl], [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, COD = 1,5-cyclooctadiene] with pyridazine (pdz) and phthalazine (phth) results in the formation of [Ir(COD)(IMes)(pdz)]Cl and [Ir(COD)(IMes)(phth)]Cl. These two complexes are shown by nuclear magnetic resonance (NMR) studies to undergo a haptotropic shift which interchanges pairs of protons within the bound ligands. When these complexes are exposed to hydrogen, they react to form [Ir(H)2(COD)(IMes)(pdz)]Cl and [Ir(H)2(COD)(IMes)(phth)]Cl, respectively, which ultimately convert to [Ir(H)2(IMes)(pdz)3]Cl and [Ir(H)2(IMes)(phth)3]Cl, as the COD is hydrogenated to form cyclooctane. These two dihydride complexes are shown, by NMR, to undergo both full N-heterocycle dissociation and a haptotropic shift, the rates of which are affected by both steric interactions and free ligand pKa values. The use of these complexes as catalysts in the transfer of polarisation from para-hydrogen to pyridazine and phthalazine via signal amplification by reversible exchange (SABRE) is explored. The possible future use of drugs which contain pyridazine and phthalazine motifs as in vivo or clinical magnetic resonance imaging probes is demonstrated; a range of NMR and phantom-based MRI measurements are reported.
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影响因子：
2.6
作者：
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通讯作者：
SIK, V
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Shaw, AA
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Mewis, Ryan E.