Golden Melissa L, Yarbrough Jason C, Reibenspies Joseph H, Darensbourg Marcetta Y
Texas A&M University, Department of Chemistry, College Station, Texas 77843, USA.
Inorg Chem. 2004 Jul 26;43(15):4702-7. doi: 10.1021/ic049387n.
The cis-dithiolate N2S2Ni complex bismercaptoethanediazacycloheptanenickel(II), (bme-dach)Ni or Ni-1', takes up two equivalents of sulfur dioxide in which thiolate-sulfur to SO2-sulfur interactions are well-defined by X-ray crystallography. Ni-1' x 2SO2, C9H18N2NiO4S4, yields monoclinic crystals belonging to the P2(1)/c space group: a = 10.308(4) angstroms, b = 13.334(5) angstroms, c = 10.842(4) angstroms, alpha = 90 degrees, beta = 91.963(6) degrees, gamma = 90 degrees, and Z = 4. Further characterization by nu(SO) IR spectroscopy, thermal gravimetric analysis, electronic spectroscopy, and visual color changes upon reversible SO2 adduct formation establish Ni-1' and the analogous bismercaptoethanediazacyclooctane derivative, (bme-daco)Ni, Ni-1, to be viable candidates for technical development as chemical sensors of this noxious gas. Visual SO2 detection limits of Ni-1 and Ni-1' are established at 25 and 100 ppm, respectively. Both the Ni-1' x 2SO2 adduct and the Ni-1' reactant are air stable. In addition, the stability of Ni-1' x SO2 to vacuum and removal of SO2 by heating make Ni-1' a possible storage/controlled release complex for SO2 gas.
顺式二硫醇盐N2S2Ni配合物双巯基乙二氮杂环庚烷镍(II)，(bme-dach)Ni或Ni-1'，能吸收两当量的二氧化硫，其中硫醇盐硫与SO2硫之间的相互作用通过X射线晶体学得到了很好的确定。Ni-1'·2SO2，C9H18N2NiO4S4，生成属于P2(1)/c空间群的单斜晶体：a = 10.308(4)埃，b = 13.334(5)埃，c = 10.842(4)埃，α = 90°，β = 91.963(6)°，γ = 90°，Z = 4。通过ν(SO)红外光谱、热重分析、电子光谱以及可逆形成SO2加合物时的视觉颜色变化进行的进一步表征表明，Ni-1'以及类似的双巯基乙二氮杂环辛烷衍生物(bme-daco)Ni，即Ni-1，是作为这种有害气体的化学传感器进行技术开发的可行候选物。Ni-1和Ni-1'的视觉SO2检测限分别确定为25 ppm和100 ppm。Ni-1'·2SO2加合物和Ni-1'反应物在空气中均稳定。此外，Ni-1'·SO2对真空的稳定性以及通过加热去除SO2使得Ni-1'成为SO2气体的一种可能的储存/控释配合物。
