Liang Binyong, Wang Xuefeng, Andrews Lester
Department of Chemistry, University of Virginia, P.O. Box 400319, Charlottesville, Virginia 22904-4319, USA.
J Phys Chem A. 2009 May 7;113(18):5375-84. doi: 10.1021/jp900994c.
Small sulfur molecules were reacted with laser-ablated Fe, Ru, and Os atoms in excess argon and condensed at 7 K. Reaction products were identified from matrix infrared spectra through sulfur-34 isotopic shifts, spectra of sulfur isotopic mixtures, and frequencies from density functional calculations. The strongest absorptions of the MS(2) disulfide molecules are observed at 540.2, 535.5, and 537.5 cm(-1), respectively, for the group 8 metals, and a 523.2 cm(-1) band is assigned to the FeS vibrational fundamental in solid argon. The FeS(2)(-) anion was detected in the spectrum at 542.1 cm(-1). The RuS(2) absorption exhibited resolved natural ruthenium isotopic splittings. Evidence is also presented for side-bound M(S(2)) isomers and MS(4) molecules with different structures including Fe(S(2))(2), (S(2))RuS(2), and tetrahedral OsS(4). Although OsO(4) is a well-known molecule, this, we believe, is the first experimental observation of OsS(4).
小的硫分子在过量氩气中与激光烧蚀的铁、钌和锇原子发生反应，并在7K下冷凝。通过硫-34同位素位移、硫同位素混合物的光谱以及密度泛函计算得到的频率，从基质红外光谱中鉴定出反应产物。对于第8族金属，二硫化物分子MS₂的最强吸收分别在540.2、535.5和537.5cm⁻¹处观察到，并且在523.2cm⁻¹处的一个谱带被指定为固态氩中FeS的振动基频。在光谱中542.1cm⁻¹处检测到FeS₂⁻阴离子。RuS₂的吸收表现出分辨出的天然钌同位素分裂。还给出了侧键合M(S₂)异构体和具有不同结构的MS₄分子的证据，包括Fe(S₂)₂、(S₂)RuS₂和四面体OsS₄。尽管OsO₄是一个知名分子，但我们认为这是OsS₄的首次实验观测。
