Synthesis and reactivity of organosamarium diarylpnictide complexes: Cleavage reactions of group 15 E-E and E-C bonds by samarium(II)
Synthesis and reactivity of organosamarium diarylpnictide complexes: Cleavage reactions of group 15 E-E and E-C bonds by samarium(II)
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DOI：
10.1021/ic951627z
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发表时间：
1996-07-17
影响因子：
4.6
通讯作者：
Khan, SI
中科院分区：
文献类型：
--
作者：
Evans, WJ;Leman, JT;Khan, SI
（C（5）Me（5））（2）Sm（2当量）与Ph（2）EEPh（2）反应得到（C（5）Me（5））（2）SmEPh（2）（E：P，1; As，2），而（C（5）Me（5））（2）Sm（THF）（2当量）与Ph（2）EEPh（2）反应得到（C（5）Me（5））（2）Sm（EPh（2））（THF）（E：P，3; As，4）。3和4也可从1和2与THF的反应中获得。3和4进一步反应生成THF开环产物（C（5）Me（5））（2）Sm[O（CH 2）（4）EPh（2）]（THF）（E：P，5; As，6）。（C（5）Me（5））（2）Sm（4 equiv）与Ph（2）EEPh（2）反应生成混合价的（C（5）Me（5））（2）Sm（mu-EPh（2））Sm（C（5）Me（5））（2）（E：P，7; As，8）。这些化合物也可从1和2与（C（5）Me（5））（2）Sm的反应中获得。从己烷中结晶的2的X射线晶体结构（P2（1）/n; a 26.188（24）埃，B = 9.911（10）埃，c = 23.280（23）埃，β = 97.150（12）度，V = 5995（2）埃（3），D-计算值= 1.488 Mg/m（3）; Z = 8; T = 156 K），揭示了除了具有2.698埃Sm-C（C（5）Me（5））和2.970埃Sm-As平均距离的常规七配位弯曲茂金属几何结构之外，两个非常不同的Sm-As-C（Ph）角，74.2和118.7度0。结果，一个苯基更接近金属（2.901埃的最小Sm-C距离）。4，从甲苯中结晶（P2（1）/n; a 10.713（9）埃，B = 14.143（11）埃，c 21.620（16）埃，β = 101.08（6）度，V = 3215（4）埃（3），D-计算值= 1.492 Mg/m（3）; Z = 4; T = 163 K）和6（P2（1）/n; a 9.3958（16）埃，B = 22.245（3）埃，c 17.931（3）埃，β = 96.497（11）度，V = 3724（1）埃（3），D-计算值= 1.416 Mg/m（3）; Z = 4; T = 163 K），具有常规的八配位、弯曲的茂金属结构。
(C(5)Me(5))(2)Sm (2 equiv) reacts with Ph(2)EEPh(2) to give (C(5)Me(5))(2)SmEPh(2) (E: P, 1; As, 2), while (C(5)Me(5))(2)Sm(THF)(2) (2 equiv) reacts with Ph(2)EEPh(2) to give (C(5)Me(5))(2)Sm(EPh(2))(THF) (E: P, 3; As, 4). 3 and 4 are also available from the reactions of 1 and 2 with THF. 3 and 4 undergo further reaction to produce the THF ring-opened products (C(5)Me(5))(2)Sm[O(CH2)(4)EPh(2)](THF) (E: P, 5; As, 6). (C(5)Me(5))(2)Sm (4 equiv) reacts with Ph(2)EEPh(2) to give the mixed-valent (C(5)Me(5))(2)Sm(mu-EPh(2))Sm(C(5)Me(5))(2) (E: P, 7; As, 8). These compounds are also available from the reaction of 1 and 2 with (C(5)Me(5))(2)Sm. The X-ray crystal structure of 2, crystallized from hexanes (P2(1)/n; a 26.188(24) Angstrom, b = 9.911(10) Angstrom, c = 23.280(23) Angstrom, beta = 97.150(12)degrees V = 5995(2) Angstrom(3), D-calcd = 1.488 Mg/m(3); Z = 8; T = 156 K), revealed, in addition to a conventional seven-coordinate bent metallocene geometry with 2.698 Angstrom Sm-C(C(5)Me(5)) and 2.970 Angstrom Sm-As average distances, two very different Sm-As-C(Ph) angles, 74.2 and 118.7 degrees 0. As a result, one phenyl group is closer to the metal (2.901 Angstrom minimum Sm-C distance). 4, crystallized from toluene (P2(1)/n; a 10.713(9) Angstrom, b = 14.143(11) Angstrom, c 21.620(16) Angstrom, beta = 101.08(6)degrees, V = 3215(4) Angstrom(3), D-calcd = 1.492 Mg/m(3); Z = 4; T = 163 K), and 6, crystallized from-hexanes (P2(1)/n; a 9.3958(16) Angstrom, b = 22.245(3) Angstrom, c 17.931(3) Angstrom, beta = 96.497(11)degrees, V = 3724(1) Angstrom(3), D-calcd = 1.416 Mg/m(3); Z = 4; T = 163 K), have conventional eight-coordinate, bent metallocene structures.