Synthesis, Molecular and Electronic Structure, and TDDFT and TDDFT-PCM Study of the Solvatochromic Properties of (Me2Pipdt)Mo(CO)4 Complex (Me2Pipdt = N,N
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- 作者：Victor N. Nemykin ; Joseph G. Olsen ; Eranda Perera ; and Partha Basu
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：May 1, 2006
- 年：2006
- 卷：45
- 期：9
- 页码：3557 - 3568
- 全文大小：386K
- 年卷期：v.45,no.9(May 1, 2006)
- ISSN：1520-510X
文摘
The synthesis, spectroscopic, and structural characterization of the (Me2Pipdt)Mo(CO)4 complex (Me2Pipdt = N,N'-piperazine-2,3-dithione) are presented in this paper. The title complex crystallizes in the P21/n space group with a= 25.541(3) Å, b = 10.3936(14) Å, c = 10.9012(12) Å, 
= 92.261(9)
, V = 2891.6(6) Å3, and Z = 8. Gas- andsolution-phase structural and electronic features of (Me2Pipdt)Mo(CO)4 and Me2Pipdt have been investigated usingdensity functional theory. The molecular structure underscores the flexibility of the NC(S)C(S)N fragment in boththe free ligand and the metal complex. On the basis of structural, spectroscopic, and theoretical results, the bidentateligand in (Me2Pipdt)Mo(CO)4 is considered to be in the dithione, not dithiolate, form. Time-dependent density functionaltheory has been used for the investigation of the excited states and solvatochromic properties of (Me2Pipdt)Mo(CO)4. The calculated vertical excitation energies in solution are consistent with the experimental data, showingthat the metal-to-ligand charge-transfer transitions, in both the visible and UV regions, dominate over the ligand-based 
-* transitions.
= 92.261(9), V = 2891.6(6) Å3, and Z = 8. Gas- andsolution-phase structural and electronic features of (Me2Pipdt)Mo(CO)4 and Me2Pipdt have been investigated usingdensity functional theory. The molecular structure underscores the flexibility of the NC(S)C(S)N fragment in boththe free ligand and the metal complex. On the basis of structural, spectroscopic, and theoretical results, the bidentateligand in (Me2Pipdt)Mo(CO)4 is considered to be in the dithione, not dithiolate, form. Time-dependent density functionaltheory has been used for the investigation of the excited states and solvatochromic properties of (Me2Pipdt)Mo(CO)4. The calculated vertical excitation energies in solution are consistent with the experimental data, showingthat the metal-to-ligand charge-transfer transitions, in both the visible and UV regions, dominate over the ligand-based -* transitions.