SYNTHETIC, STRUCTURAL, AND REACTIVITY STUDIES OF THE REDUCTION AND CO DERIVATIZATION OF AZOBENZENE MEDIATED BY DIVALENT LANTHANIDE COMPLEXES
SYNTHETIC, STRUCTURAL, AND REACTIVITY STUDIES OF THE REDUCTION AND CO DERIVATIZATION OF AZOBENZENE MEDIATED BY DIVALENT LANTHANIDE COMPLEXES
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DOI：
10.1021/ja00223a016
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发表时间：
1988-07-20
影响因子：
15
通讯作者：
ATWOOD, JL
中科院分区：
文献类型：
--
作者：
EVANS, WJ;DRUMMOND, DK;ATWOOD, JL
在甲苯中以 1:1 的比例将 (C5Me5) 2Sm (THF) 2 添加到 C6H5N= NC6H5 中，形成绿色 (C5Me5) 2Sm (t72-N2Ph2)(THF)(1)。在甲苯中以1:2的比例将偶氮苯添加到(C5Me5) 2Sm (THF) 2 中，形成蓝色[(C5Me5) 2Sm] 2 (N2Ph2)(2)。在THF中，2慢慢转变成[(C5Me5)(THF) Sm] 2 [u-? j2:tj2-N2Ph2]2(3)。配合物1-3均具有与偶氮苯衍生的配体的氮原子配位的三价(C5Me5)ISm部分。在 1 中，氮原子与 Sm 配位，平均 Sm-N 距离为 2.42 (2) A。在 2 中，一个 (C5Me5) 2Sm 基团以反式方向连接到每个氮原子，Sm-N 距离为 2.40 (1) 和 2.41 (1) A。在 3 中，每个 (C5Me5) Sm 单元与具有 Sm-N 的两个 N2Ph2 单元相互作用。每个的距离为 2.323 (8) 和 2.559 (7) A。 NN 距离为 1 中的 1.35 (2) A（平均）、2 中的 1.25 (1) A 和 3 中的 1.44 (1) A。在 THF 中以 1:2 的比例将偶氮苯添加到 (C5H5) 2Yb (THF) 中，形成绿色溶液，该溶液沉积 [(C5H5)(THF) Yb] 2 [M-»! 2：n2-N2Ph2] 2 (4) 和 Cp3Yb (THF)。 4 的结构类似于 3。4 的 Yb-N 距离为 2.188 (5)、2.206 (5)、2.487 (5) 和 2.572 (5) A，NN 长度为 1.470 (6) A。配合物 1 在 70 psi 下无法与 CO 反应，但 2 反应形成 [(C5Me5) 2Sm] 2 [ju-774-(PhN) OCCO (NPh)](5)。在 5 中，两个三价 (C5Me5) 2Sm 单元通过双去质子化/Vj/V'-二苯基草酰胺配体分别通过 2.49 (1) 和 2.30 (1) A 的 Sm-N 和 Sm-O 键桥接。(C5Me5) 2Sm (THF) 2 与 3, 3'-偶氮甲苯反应形成 6，其类似物2. 6 与 CO 反应形成 7，5 的类似物。CO 与 2 和 6 的等摩尔混合物反应，完全生成 5 和 7，没有交叉产物 [(C5Me5) 2Sm] 2 [M-t74"(PhN) OCCO (NC6H4Me-3)]。类似地 [(C5Me5) 2Sm] 2-(PhNNC6H4NMe2-4) 与 CO 反应生成 [(C5Me5) 2Sm] 2 [(PhN) OCCO (NC6H4NMe2-4)] 络合物 1 在 34℃ 下从己烷/THF 中结晶，PI 空间群中每两个分子式结晶有一个 THF 分子，a= 10.732 (4) k，b= 19.548 (9) A, c= 19.892 (10) A, a= 110.14 (4), 0= 104.75 (4), y= 101.21 (3), Z= 4 (Z) calcd= 1.31 g cm" 3. 基于 6906 个观测反射的最小二乘精修得出最终 R 值为 0.066。配合物 2 在空间群 P2\jn 中从甲苯中结晶至 34 C，其中 a= 10.855 (7) k、b= 20.435 (5) A、c= 21.686 (9) A、0= 106.68 (4)，对于 Z= 4 二聚体，Aakd= 1-48 g cm" 3。基于以下的最小二乘精修4130 次观察到的反射导致最终 R 值为 0.033。配合物 3 在 28-30°C 下从 THF 中结晶，具有空间群 C2/m 中的两个 THF 结晶分子，其中 a= 22.409 (8) k、b= 13.178 (5) A、c= 9.978 (4) A、0= 108.84 (5) 和 Z) calcd= 1.46 g cm" 3 对于 Z= 2（每个晶胞 2 个二聚体）。基于 1278 个观察到的反射的最小二乘细化得出最终 R 值为 0.038。配合物 4 由甲苯结晶而成，甲苯结晶分子处于空间群 PI 中，a= 9.645 (2) k，b= 11.369 (3) A，c= 10.143 (5) k，a= 97.33 (3)，0= 94.36 (3)，y= 93.18 (2)，和/)计算值= 1.62 g cm" 3（Z= 1）。基于 3239 次观察到的反射进行最小二乘精修，最终 R 值为 0.030。络合物 5 在 34 C 下从甲苯中结晶，甲苯结晶分子处于空间群 A2/m 中，a= 15.961 (3) A、b= 14.204 (5) k、c= 15.612 (8) A, 0= 118.14 (3)，且 Z> calc<|= 1.25 g cm" 3（对于 Z= 2）。基于 2151 个观察到的反射的最小二乘细化导致最终 R 值为 0.053。
The addition of (C5Me5) 2Sm (THF) 2 to C6H5N= NC6H5 in a 1: 1 ratio in toluene forms green (C5Me5) 2Sm (t72-N2Ph2)(THF)(1). The addition of azobenzene to (C5Me5) 2Sm (THF) 2 in a 1: 2 ratio in toluene forms blue [(C5Me5) 2Sm] 2 (N2Ph2)(2). InTHF, 2 slowly transforms into [(C5Me5)(THF) Sm] 2 [u-? j2: tj2-N2Ph2] 2 (3). Complexes 1-3 all have trivalent (C5Me5) ISm moieties coordinated to nitrogen atoms of ligands derived from azobenzene. In 1, the nitrogen atoms are^-coordinated to Sm with an average Sm-N distance of 2.42 (2) A. In 2, one (C5Me5) 2Sm group is attached to each nitrogen atom in a trans orientation with Sm-N distances of 2.40 (1) and 2.41 (1) A. In 3, each (C5Me5) Sm unit interacts with both N2Ph2 units with Sm-N distances of 2.323 (8) and 2.559 (7) A to each. The NN distances are 1.35 (2) A (average) in 1, 1.25 (1) A in 2, and 1.44 (1) A in 3. Addition of azobenzene to (C5H5) 2Yb (THF) in a 1: 2 ratio in THF forms a green solution which deposits crystals of [(C5H5)(THF) Yb] 2 [M-»! 2: n2-N2Ph2] 2 (4) and Cp3Yb (THF). Thestructure of 4 is analogous to that of 3. 4 has Yb-N distances of 2.188 (5), 2.206 (5), 2.487 (5), and 2.572 (5) A and an NN length of 1.470 (6) A. Complex 1 fails to react with CO at 70 psi but 2 reacts to form [(C5Me5) 2Sm] 2 [ju-774-(PhN) OCCO (NPh)](5). In 5, the two trivalent (C5Me5) 2Sm units are bridged by a doubly deprotonated/Vj/V'-diphenyloxamide ligand via Sm-N and Sm-O bonds of 2.49 (1) and 2.30 (1) A, respectively.(C5Me5) 2Sm (THF) 2 reacts with 3, 3'-azotoluene to form 6, an analogue of 2. 6 reacts with CO to form 7, an analogue of 5. Reaction of CO with an equimolar mixture of 2 and 6 gives 5 and 7exclusively with no evidence of the crossover product [(C5Me5) 2Sm] 2 [M-t74"(PhN) OCCO (NC6H4Me-3)]. Similarly [(C5Me5) 2Sm] 2-(PhNNC6H4NMe2-4) reacts with CO to form [(C5Me5) 2Sm] 2 [(PhN) OCCO (NC6H4NMe2-4)] exclusively. Complex 1 crystallizes from hexane/THF at-34 C with one THF molecule of crystallization per two formula units in space group PI with a= 10.732 (4) k, b= 19.548 (9) A, c= 19.892 (10) A, a= 110.14 (4), 0= 104.75 (4), y= 101.21 (3), and Z= 4 for Z) calcd= 1.31 g cm" 3. Least-squares refinement on the basis of 6906 observed reflections led to a final R value of 0.066. Complex 2 crystallizes from tolueneat-34 C in space group P2\jn with a= 10.855 (7) k, b= 20.435 (5) A, c= 21.686 (9) A, 0= 106.68 (4), and Aakd= 1-48 g cm" 3 for Z= 4 dimers. Least-squares refinement on the basis of 4130 observed reflections led to a final R value of 0.033. Complex 3 crystallizes from THF at 28-30 C with two THF molecules of crystallization in space group C2/m with a= 22.409 (8) k, b= 13.178 (5) A, c= 9.978 (4) A, 0= 108.84 (5), and Z) calcd= 1.46 g cm" 3 for Z= 2 (2 dimers per unit cell). Least-squares refinement on the basis of 1278 observed reflections led to a final R value of 0.038. Complex 4 crystallizesfrom toluene with a toluene molecule of crystallization in space group PI with a= 9.645 (2) k, b= 11.369 (3) A, c= 10.143 (5) k, a= 97.33 (3), 0= 94.36 (3), y= 93.18 (2), and/) calcd= 1.62 g cm" 3 for Z= 1. Least-squares refinement on the basis of 3239 observed reflections led to a final R value of 0.030. Complex 5 crystallizes from tolueneat-34 C with a toluene molecule of crystallization in space group A2/m with a= 15.961 (3) A, b= 14.204 (5) k, c= 15.612 (8) A, 0= 118.14 (3), and Z> calc<|= 1.25 g cm" 3 for Z= 2. Least-squares refinement on the basis of 2151 observed reflections led to a final Rvalue of 0.053.