CEA, IRAMIS, SIS2M, CNRS UMR 3299, CEA/Saclay, 91191 Gif-sur-Yvette, France.
Inorg Chem. 2011 Dec 5;50(23):12204-14. doi: 10.1021/ic201994w. Epub 2011 Nov 3.
In contrast to the neutral macrocycle [UN*(2)(N,C)] (1) [N* = N(SiMe(3))(3); N,C = CH(2)SiMe(2)N(SiMe(3))] which was quite inert toward I(2), the anionic bismetallacycle [NaUN*(N,C)(2)] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me(3)Si)NSiMe(2)CH(2)CH(2)SiMe(2)N(SiMe(3))] resulting from C-C coupling of the two CH(2) groups, and [NaUN*(N,O)(2)] (3) [N,O = OC(═CH(2))SiMe(2)N(SiMe(3))], which is devoid of any U-C bond, was oxidized into the U(V) bismetallacycle [Na{UN*(N,O)(2)}(2)(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN(3) or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN*(2)(N,C)(N(3))] [M = Na, 7a or Na(15-crown-5), 7b], M[UN*(2)(N,C)(CN)] [M = NEt(4), 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N(3))(2)] [M = Na, 9a or Na(THF)(4), 9b], [NEt(4)][UN*(N,N)(CN)(2)] (10), M[UN*(N,O)(2)(N(3))] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O)(2)(CN)] [M = NEt(4), 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral U(V) complex [U(N{SiMe(3)}SiMe(2)C{CHI}O)(2)I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined.
与对 I(2) 相当惰性的中性大环 [UN*(2)(N,C)]（1）[N*=N(SiMe(3))(3)；N,C=CH(2)SiMe(2)N(SiMe(3))]不同，阴离子双金属环 [NaUN*(N,C)(2)]（2）很容易转化为通过两个 CH(2) 基团的 C-C 偶联生成的扩大单金属环 [UN*(N,N)I]（4）[N,N=(Me(3)Si)NSiMe(2)CH(2)CH(2)SiMe(2)N(SiMe(3))]，而不含任何 U-C 键的 [NaUN*(N,O)(2)]（3）[N,O=OC(═CH(2))SiMe(2)N(SiMe(3))]则被氧化为 U(V) 双金属环 [Na{UN*(N,O)(2)}(2)(μ-I)]（5）。4 通过钠汞齐还原得到 U(III)化合物 [UN*(N,N)]（6）。将 MN(3)或 MCN 添加到 (N,C)、(N,N)和 (N,O)金属环 1、4 和 5 中，形成了阴离子叠氮化物或氰化物衍生物 M[UN*(2)(N,C)(N(3))] [M=Na，7a 或 Na(15-冠-5)，7b]，M[UN*(2)(N,C)(CN)] [M=NEt(4)，8a 或 Na(15-冠-5)，8b 或 K(18-冠-6)，8c]，M[UN*(N,N)(N(3))(2)] [M=Na，9a 或 Na(THF)(4)，9b]，[NEt(4)][UN*(N,N)(CN)(2)]（10），M[UN*(N,O)(2)(N(3))] [M=Na，11a 或 Na(15-冠-5)，11b]，M[UN*(N,O)(2)(CN)] [M=NEt(4)，12a 或 Na(15-冠-5)，12b]。在 THF 中存在过量碘时，氰化物 12a 被转化回碘化物 5，而叠氮化物 11a 转化为中性 U(V) 配合物 [U(N{SiMe(3)}SiMe(2)C{CHI}O)(2)I(THF)]（13）。确定了 4、7b、8a-c、9b、10、12b 和 13 的 X 射线晶体结构。
