Wu Jingcun, Bancroft G. Michael, Puddephatt Richard J., Hu Y. F., Li Xiaorong, Tan K. H.
Department of Chemistry, University of Western Ontario, London, Ontario, Canada N6A 5B7, and Canadian Synchrotron Radiation Facility, University of Wisconsin-Madison, Stoughton, Wisconsin 53589.
Inorg Chem. 1999 Oct 18;38(21):4688-4695. doi: 10.1021/ic9904687.
High-resolution broad-scan gas-phase photoelectron spectra using synchrotron radiation (including valence, inner valence, and core levels) are reported for a series of trimethylphosphine-substituted tungsten carbonyls: W(CO)(6), W(CO)(5)PMe(3), cis-W(CO)(4)(PMe(3))(2), trans-W(CO)(4)(PMe(3))(2), and fac-W(CO)(3)(PMe(3))(3). The inner valence and core level spectra are interpreted by comparison with the published spectra of W(CO)(6) and other metal carbonyls. High-resolution valence level spectra of these complexes are also obtained by He I radiation. Fine structure, resulting from spin-orbit splitting, ligand field splittings, and vibrational coupling is resolved in the spectra of both W 5d and W 4f regions. Ligand field splittings on both the W 5d and W 4f levels increase in the order W(CO)(6) approximately fac-W(CO)(3)(PMe(3))(3) < W(CO)(5)PMe(3) </= cis-W(CO)(4)(PMe(3))(2) < trans-W(CO)(4)(PMe(3))(2). For the first time, the phosphorus 2p spin-orbit components of the phosphine complexes have been resolved. The binding energies (or ionization potentials) in the spectra of both W 5d valence level and W 4f core level regions are shifted almost linearly to lower energy with each successive step of ligand substitution. The shift per phosphine substitution is 0.66 +/- 0.03 eV for the W 5d ionizations and 0.76 +/- 0.03 eV for the W 4f ionizations (DeltaE(valence)/DeltaE(core) = 0.86 +/- 0.03). Similar linear shift trends are also found in the phosphorus 2p core level and phosphorus valence "lone-pair" ionizations. These data confirm the ligand additivity model predictions for these complexes.
报道了一系列三甲基膦取代的羰基钨化合物（W(CO)₆、W(CO)₅PMe₃、顺式-W(CO)₄(PMe₃)₂、反式-W(CO)₄(PMe₃)₂和 fac-W(CO)₃(PMe₃)₃）使用同步辐射的高分辨率宽扫描气相光电子能谱（包括价电子、内层价电子和芯能级）。通过与已发表的 W(CO)₆和其他金属羰基化合物的能谱进行比较来解释内层价电子和芯能级能谱。这些配合物的高分辨率价电子能级能谱也通过 He I 辐射获得。在 W 5d 和 W 4f 区域的能谱中都分辨出了由自旋轨道分裂、配体场分裂和振动耦合产生的精细结构。W 5d 和 W 4f 能级上的配体场分裂按 W(CO)₆≈ fac-W(CO)₃(PMe₃)₃ < W(CO)₅PMe₃≤顺式-W(CO)₄(PMe₃)₂ < 反式-W(CO)₄(PMe₃)₂的顺序增加。膦配合物的磷 2p 自旋轨道成分首次得到分辨。随着配体取代的每一步，W 5d 价电子能级和 W 4f 芯能级区域能谱中的结合能（或电离能）几乎线性地向低能方向移动。对于 W 5d 电离，每次膦取代的移动量为 0.66±0.03 eV，对于 W 4f 电离为 0.76±0.03 eV（ΔE(价电子)/ΔE(芯能级)=0.86±0.03）。在磷 2p 芯能级和磷价“孤对”电离中也发现了类似的线性移动趋势。这些数据证实了这些配合物的配体加和模型预测。
