Chemistry Department, Florida Institute of Technology, 150 University Boulevard, Melbourne, FL 32901, USA.
Dalton Trans. 2013 Nov 28;42(44):15617-24. doi: 10.1039/c3dt51758f.
Hypodentate diamine cobalt(III) pentammine complexes Co(NH3)5(NH2(CH2)(n)NH3)4 (8: a: n = 3; b: n = 4; c: n = 6; d: n = 8) have been synthesized via the reaction of Co(NH3)5(OTf)2 (TfOH = CF3SO3H) with the corresponding diamines. The analogous t-boc protected diamine complexes Co(NH3)5(NH2(CH2)(n)NHt-boc)3 (7a-d) were prepared in 4-26% yield. Low yields for the formation of 7a-d are due to competing side reactions which also gave Co(NH3)6. Complexes 7a-d were deprotected using trifluoroacetic acid to give the corresponding hypodentate diamine complexes Co(NH3)5(NH2(CH2)(n)NH3)0.5(ClO4)3.5 (9a-d). HBTU coupling of 8c with N-(t-boc)-L-phenylalanine gave an amino acid functionalized cobalt pentammine complex Co(NH3)5(NH2(CH2)6NHt-boc)-L-phenylalanine)3 (10). All new complexes were characterized using UV-vis and (1)H NMR spectroscopy, and elemental analysis. Grafting of 8c onto 2.4 mm poly(ethylene-co-acrylic acid) (PEAA) beads was achieved via amide coupling. Complex 8c was coupled to thioctic acid via amide coupling and the resulting cobalt disulfide complex Co(NH3)5(N-(6-aminohexyl)-5-(1,2-dithiolan-3-yl)pentanamide)3 (11) was attached to 10 nm Au nanoparticles. The amount of cobalt loading onto PEAA beads and Au nanoparticles was determined using ICP-MS and EDX.
通过Co(NH3)5(OTf)2 (TfOH = CF3SO3H)与相应的二胺反应，合成了缺齿二胺钴(III)五氨配合物Co(NH3)5(NH2(CH2)(n)NH3)4 (8：a：n = 3；b：n = 4；c：n = 6；d：n = 8)。相应的 t-boc 保护二胺配合物Co(NH3)5(NH2(CH2)(n)NHt-boc)3 (7a-d)以 4-26%的产率制备。7a-d 的形成产率低是由于竞争的副反应也产生了Co(NH3)6。使用三氟乙酸对 7a-d 进行脱保护，得到相应的缺齿二胺配合物Co(NH3)5(NH2(CH2)(n)NH3)0.5(ClO4)3.5 (9a-d)。8c 与 N-(t-boc)-L-苯丙氨酸的 HBTU 偶联得到氨基酸功能化的钴五氨配合物Co(NH3)5(NH2(CH2)6NHt-boc)-L-苯丙氨酸)3 (10)。所有新配合物均通过紫外可见光谱和(1)H NMR 光谱以及元素分析进行了表征。通过酰胺偶联将 8c 接枝到 2.4mm 聚(乙烯-co-丙烯酸)(PEAA)珠上。通过酰胺偶联将 8c 与硫辛酸偶联，得到钴二硫化物配合物Co(NH3)5(N-(6-氨基己基)-5-(1,2-二硫戊环-3-基)戊酰胺)3 (11)，并将其连接到 10nm Au 纳米粒子上。通过 ICP-MS 和 EDX 测定 PEAA 珠和 Au 纳米粒子上的钴负载量。
