New synthetic routes to a disulfidodinickel(II) complex:: Characterization and reactivity of a Ni2(μ-η2:η2-S2) core
New synthetic routes to a disulfidodinickel(II) complex:: Characterization and reactivity of a Ni2(μ-η2:η2-S2) core
复制标题
DOI：
10.1021/ic800321x
复制
发表时间：
2008-05-19
影响因子：
4.6
通讯作者：
Riordan, Charles G.
中科院分区：
文献类型：
--
作者：
Cho, Jaeheung;Van Heuvelen, Katherine M.;Riordan, Charles G.
通过单价镍络合物[PhTt（tBu）]Ni（CO）[PhTt（tBu）=苯基{三[（叔丁基甲基）硫基]甲基}硼酸酯]活化元素硫产生二硫代二镍（II）络合物2。这种物质可通过[PhTt（tBu）]Ni（SCPh 3）的热分解来替代。光谱、磁性和X射线衍射研究证实2含有一个μ-eta（2）：eta（2）-S-2配体，它促进了Ni-II离子之间的反铁磁交换耦合。这一观察结果与较轻的同系物氧形成对比，氧强烈倾向于双（μ-氧代）二镍（III）结构。2将PPh 3氧化成SPPh 3并与O2反应，生成几种产物，其中一种已被鉴定为[（PhTt（tBu））Ni]（2）（mu-S）（3）。
Activation of elemental sulfur by the monovalent nickel complex [PhTt(tBu)]Ni(CO) [PhTt(tBu) = phenyl{tris[(tert-butylmethyl)thio]methyl}borate] generates the disulfidodinickel(II) complex 2. This species is alternatively accessible via thermal decomposition of [PhTt(tBu)]Ni(SCPh3). Spectroscopic, magnetic, and X-ray diffraction studies establish that 2 contains a mu-eta(2):eta(2)-S-2 ligand that fosters antiferromagnetic exchange coupling between the Ni-II ions. This observation is in contrast to the lighter congener, oxygen, which strongly favors the bis(mu-oxo)dinickel(III) structure. 2 oxidizes, PPh3 to SPPh3 and reacts with 02, generating several products, one of which has been identified as [(PhTt(tBu))Ni](2)(mu-S) (3).