GENERATION OF (2,3-ETA)-NAPHTHALYNE-NICKEL(0) COMPLEXES AND THEIR REACTIONS WITH UNSATURATED MOLECULES
GENERATION OF (2,3-ETA)-NAPHTHALYNE-NICKEL(0) COMPLEXES AND THEIR REACTIONS WITH UNSATURATED MOLECULES
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DOI：
10.1021/om00004a071
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发表时间：
1995-04-01
期刊：
影响因子：
2.8
通讯作者：
WENGER, E
中科院分区：
文献类型：
--
作者：
BENNETT, MA;HOCKLESS, DCR;WENGER, E
用钠汞齐还原3-溴萘基镍（II）配合物NiBr（3-Br-2-C10 H6）L（2），得到第一个2，3-萘乙炔的单体镍（0）配合物Ni（eta（2）-C10 H6）L（2）（2 L = 2 PEt（3）（2），dcpe（5）; dcpe = 1，2-双（二环己基膦基）乙烷，Cy（2）PCH（2）CH（2）PCy（2））。配合物2分别与二苯乙炔和乙炔二甲酯发生双插入反应，得到1，2，3，4-四取代蒽，C（14）H（6）R（4）（R = CO（2）Me（8），Ph（9））。配合物5与CO_2和C_2F_4反应，分别得到单插入萘-镍（0）键的产物Ni（3-C_10H_6COO-2）（dcpe）（6）和Ni（3-C_10H_6CF_2CF_2 -2）（dcpe）（7），配合物7进一步与DMAD反应，得到Ni{3-C（CO（2）Me）=C（CO（2）Me）C_10H_6CF_2CF_2 -2}（dcpe）（10）。用重原子方法和最小二乘法对化合物6、7和10的结构进行了修正。晶体数据：6，空间群P2（1）/n（编号14），a = 14.714（2）埃，B = 17.100（1）埃，c = 15.990（2）埃，β = 110.244（9）度，Z = 4，观察到2997个反射（I > 3 σ（I）），其中R = 4.1且R（w）= 2.8; 7，空间群P2（1）/c（编号14），a = 11.139（2）埃，B = 19.557（2）埃，c = 16.809（2）埃，β = 92.927（9）度，Z = 4，3872个观察到的反射（I > 3 σ（I）），其中R = 3.5且R（w）= 2.9; 10，棒1上的空间群P（$）（编号2），a = 9.415（3）埃，B = 11.759（2）埃，c = 20.218（3）埃，α = 93.94（1）度，β = 94.77（2）度，γ 108.90（2）度，Z = 2，4432个观察到的反射（I > 3 sigma（I）），其中R = 3.6且R（w）= 3.0。
Sodium-amalgam reduction of the (3-bromonaphthyl)nickel(II) complexes NiBr(3-Br-2-C10H6)L(2) gives the first monomeric nickel(0) complexes of 2,3-naphthalyne, Ni(eta(2)-C10H6)L(2) (2 L = 2 PEt(3) (2), dcpe (5); dcpe = 1,2-bis(dicyclohexylphosphino)ethane, Cy(2)PCH(2)CH(2)PCy(2)). Complex 2 undergoes double-insertion reactions with dimethyl acetylenedicarboxylate (DMAD) or diphenylacetylene to give 1,2,3,4-tetrasubstituted anthracenes, C(14)H(6)R(4) (R = CO(2)Me (8), Ph (9). Complex 5 reacts with CO2 and with C2F4 to give isolable products of monoinsertion into the naphthalyne-nickel(0) bond, Ni(3-C10H6COO-2)(dcpe) (6) and Ni(3-C10H6CF2CF2-2)(dcpe (7), respectively, and 7 undergoes further insertion with DMAD to give Ni{3-C(CO(2)Me)=C(CO(2)Me)C10H6CF2CF2-2}(dcpe) (10). The structures of 6, 7, and 10 have been solved by heavy-atom methods and refined by least-squares methods. Crystal data: 6, space group P2(1)/n (No. 14), a = 14.714(2) Angstrom, b = 17.100(1) Angstrom, c = 15.990(2) Angstrom, beta = 110.244(9)degrees, Z = 4, 2997 observed reflections (I > 3 sigma(I)) with R = 4.1 and R(w) = 2.8; 7, space group P2(1)/c (No. 14), a = 11.139(2) Angstrom, b = 19.557(2) Angstrom, c = 16.809(2) Angstrom, beta = 92.927(9)degrees, Z = 4, 3872 observed reflections (I > 3 sigma(I)) with R = 3.5 and R(w) = 2.9; 10, space group P ($) over bar 1 (No. 2), a = 9.415(3) Angstrom, b = 11.759(2)Angstrom, c = 20.218(3)Angstrom, alpha = 93.94(1)degrees, beta = 94.77(2)degrees, gamma 108.90(2)degrees, Z = 2, 4432 observed reflections (I > 3 sigma(I)) with R = 3.6 and R(w) = 3.0.