物理化学学报 >> 1994, Vol. 10 >> Issue (10): 887-891.doi: 10.3866/PKU.WHXB19941005

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Pt2M2异金属四核原子簇化合物成键规律探讨

林梦海, 张乾二   

  1. 厦门大学化学系物理化学研究所，厦门 361005
  • 收稿日期:1993-07-29 修回日期:1993-10-18 发布日期:1994-10-15
  • 通讯作者: 林梦海

Exploration on Bonding Regularity for Mixed-metal Four-nuclear Clusters Pt2M2

Lin Meng-Hai, Zhang Qian-Er   

  1. Department of Chemistry and Institute of Physical Chemistry,Xiamen University,Xiamen 361005
  • Received:1993-07-29 Revised:1993-10-18 Published:1994-10-15
  • Contact: Lin Meng-Hai

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摘要：

对十二个Pt_2M_2四核异金属簇化合物进行了鼻子化学DV－Xα方法的计算与讨论，探讨了这些原子簇的成键规律．它们大致可分为三类：Pt与Ⅷ族金同形成的四核簇，Pt尽量保持自己原有的价电荷；Pt与ⅥB族金属形成的原子簇，ⅥB族元素是电荷的主要提供者；Pt与IB族金属形成的原子簇，体系主要由配体PPh_3提供电荷．并提出，簇合时，三苯基膦配体起电子调节作用，环戊烯基配体起推电子作用．从能带分析，VB族或IB族金属介入原子簇，使Pt的5d能带上升或下降，其表面的吸附能力也随之发生变化.

关键词: Pt2M2, 异金属原子簇, DV-Xα方法, 电荷转移, 配体效应

Abstract:

12 mixed-metal, four-nuclear clusters Pt2M2 have been calculated and discussed using DV-Xαmethod of quantum chemistry. We studied their bonding regularity and found out that they may be classified as three types: the first kind of clusters formed from Pt and group metal are the most stable one) and Pt atom as far as possible preserves valence electrons of itself, for the second clusters, platinum mixes with group metal, ⅥB metal make major contribution of charges; in the third clusters, in which Pt and Cu, Ag, or Au present quite low electronic valences, the charges of such systems are mainly suppied by the ligand PPh3. We have also found that the triphenyl phosphine ligand is an electronic adjuster for cluster syntheses and the cyclopentadienyl ligand pushes much charges from VIB metal towards the cluster compounds. The 5d energy bands of Pt will rise or fall if ⅥB or IB metal atom interjects into the platinum c1uster. In this case, adsorption ability on the surface of mixed metal will change remarkbly clearly.

Key words: Pt2M2, Mixed-metal cluster, DV-X&alpha, method, Charge transport, Ligand effect