Synthesis, structure and reactivity of fluorovinyl nickel complexes: formation of a phosphonioethenyl complexDedicated to Professor Dieter Naumann on the occasion of his 60th birthday.
Synthesis, structure and reactivity of fluorovinyl nickel complexes: formation of a phosphonioethenyl complexDedicated to Professor Dieter Naumann on the occasion of his 60th birthday.
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氟乙烯基镍络合物的合成、结构和反应性：膦酰乙烯基络合物的形成谨献给 Dieter Naumann 教授，庆祝其 60 岁生日。
DOI：
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发表时间：
2002
期刊：
影响因子：
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通讯作者：
H. Stammler
中科院分区：
文献类型：
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作者：
T. Braun;Berit Blöcker;Verena Schorlemer;B. Neumann;A. Stammler;H. Stammler
在PEt 3存在下，[Ni（COD）2]分别与三氟碘乙烯或1，1-二溴二氟乙烯反应，生成配合物trans-[NiI（CFCF 2）（PEt 3）2]（1）和trans-[NiBr（CBrCF 2）（PEt 3）2]（2）。1与NaBAr′4和乙腈反应得到反式-[Ni（CFCF 2）（NCMe）（PEt 3）2]BAr′4（4）[Ar′
= 3，5-C6H3（CF3）2]。在CO存在下，1与NaBAr′4反应生成阳离子配合物trans-[Ni（CFCF 2）（CO）（PEt 3）2]BAr′4
(5)，仅在CH 2Cl 2溶液中稳定。1与NaBAr′4和tBuNC反应得到化合物trans-[Ni（CFCF 2）（CNTBu）（PEt 3）2]BAr′4（6）。在用NaBAr′4和PEt 3处理时，络合物6可以转化为双阳离子膦酰基乙烯基化合物trans-[Ni{CFCF（PEt 3）}（CNTBu）（PEt 3）2][BAr′4]2（7）。配合物2和配合物7的晶体结构由X-射线衍射法测定。7中的膦酰基乙烯基配体以1.893（5）A的Ni-C距离与镍结合。CC和CF-P的键长分别为1.309（6）A和1.794（5）A。
Treatment of [Ni(COD)2] with trifluoroiodoethene or 1,1-dibromodifluoroethene in the presence of PEt3 effects the formation of the complexes trans-[NiI(CFCF2)(PEt3)2] (1) and trans-[NiBr(CBrCF2)(PEt3)2] (2), respectively. Reaction of 1 with NaBAr′4 and acetonitrile gives trans-[Ni(CFCF2)(NCMe)(PEt3)2]BAr′4 (4) [Ar′
= 3,5-C6H3(CF3)2]. Treatment of 1 with NaBAr′4 in the presence of CO yields the cationic complex trans-[Ni(CFCF2)(CO)(PEt3)2]BAr′4
(5), which is only stable in a CH2Cl2 solution. The reaction of 1 with NaBAr′4 and tBuNC affords the compound trans-[Ni(CFCF2)(CNtBu)(PEt3)2]BAr′4 (6). On treatment with NaBAr′4 and PEt3 complex 6 can be converted into the dicationic phosphonioethenyl compound trans-[Ni{CFCF(PEt3)}(CNtBu)(PEt3)2][BAr′4]2 (7). The structures of complexes 2 and 7 have been determined by X-ray crystallography. The phosphonioethenyl ligand in 7 is bound at nickel with a Ni–C distance of 1.893(5) A. The CC and the CF–P bond lengths are 1.309(6) A and 1.794(5) A, respectively.