Functionalized Carborane Complexes of the [M(CO)2(NO)]2+ Core (M=99mTc, Re): A New Class of Organometallic Probes for Correlated in Vitro and in Vivo Imaging
Functionalized Carborane Complexes of the [M(CO)2(NO)]2+ Core (M=99mTc, Re): A New Class of Organometallic Probes for Correlated in Vitro and in Vivo Imaging
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DOI：
10.1021/om8011807
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发表时间：
2009-05-25
期刊：
影响因子：
2.8
通讯作者：
Valliant, John F.
中科院分区：
文献类型：
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作者：
Armstrong, Andrea F.;Lebert, Julie M.;Valliant, John F.
功能化碳硼烷配合物[M(CO)(2)(NO)](2+)(M=Re，Tc-99)作为相关光学(M=Re)和闪烁(M=TC-99m)成像的配对探针具有潜在的应用前景。本文提出了一条合成[Re(CO)(2)(NO)(RR‘C2B9H9)][Re(CO)(2)(NO)(RR’C2B9H9)]的合成路线，得到了四个新的金属碳硼烷[Re(CO)(2)(NO)(Rr‘C2B9H9)]，它们都具有3，1，2(6a：R H，R’=Bn)和2，1，8(7a：R=R‘=H；8a：R=H，R’=Ph；9a：R=R‘=Bn)笼形构型。这些配合物在300-348 nm处有较强的吸收，在300 nm(7a)或类似于340 nm(6a，8a/9a)的激发下，6a-9a在常温下有微弱的荧光，发射峰值在313-411 nm之间。用微波辅助的方法在示踪剂水平上制备了放射性[TC-99m(CO)(3)](+)-碳硼烷配合物(1b-4b)。当采用类似的水相亚硝化方法生成二羰基亚硝基技术碳硼烷时，以良好的放化产率(62-79%)分离出新的配合物6b、8b和9b。在水溶液中观察到6b和8b的缓慢分解，但没有观察到9b的分解。为了更好地了解这一过程，还制备了8a的放射性Re-186/188类似物。
Functionalized carborane complexes of the [M(CO)(2)(NO)](2+) (M = Re, Tc-99) core have potential utility as matched pairs of probes for correlated optical (M = Re) and scintigraphic (M = Tc-99m) imaging. A synthetic route to closo-rhenacarboranes of the type [Re(CO)(2)(NO)(RR'C2B9H9)] in a manner suitable for the preparation of the radioactive technetium-99m analogues has been developed, resulting in the isolation of four novel metallacarboranes [Re(CO)(2)(NO)(RR'C2B9H9)], which exhibit both 3,1,2 (6a: R H, R' = Bn) and 2,1,8 (7a: R = R' = H; 8a: R = H, R' = Ph; 9a: R = R' = Bn) cage configurations. These complexes absorb strongly at 300-348 nm; 6a-9a fluoresce weakly at ambient temperature following, excitation at 300 nm (7a) or similar to 340 nm (6a, 8a/9a), with emission maxima ranging between 313 and 411 nm. A microwave-assisted approach was used to prepare radioactive [Tc-99m(CO)(3)](+)-carborane complexes (1b-4b) at the tracer level. When an analogous aqueous nitrosation methodology was applied to generate dicarbonylnitroso-closo-technetacarboranes, the novel complexes 6b, 8b, and 9b were isolated in good radiochemical yields (62-79%). In aqueous solutions, slow decomposition of 6b and 8b, but not 9b was observed. To better understand this process, the radioactive Re-186/188 analogue of 8a was also prepared.