(Fluoren-9-ylidene)methanedithiolato Complexes of Platinum: Synthesis, Reactivity, and Luminescence1

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• 作者：José ; Vicente ; Pablo Gonz&aacute ; lez-Herrero ; Marí ; a Pé ; rez-Cadenas ; Peter G. Jones ; and Delia Bautista
• 刊名：Inorganic Chemistry
• 出版年：2005
• 出版时间：October 3, 2005
• 年：2005
• 卷：44
• 期：20
• 页码：7200 - 7213
• 全文大小：237K
• 年卷期：v.44,no.20(October 3, 2005)
• ISSN：1520-510X

文摘

Platinum(II) complexes with (fluoren-9-ylidene)methanedithiolato and its 2,7-di-tert-butyl- and 2,7-dimethoxy-substitutedanalogues were obtained by reacting different chloroplatinum(II) precursors with the piperidinium dithioates (pipH)[(2,7-R₂C₁₂H₆)CHCS₂] [R = H (1a), t-Bu (1b), or OMe (1c)] in the presence of piperidine. The anionic complexesQ₂[Pt{S₂C=C(C₁₂H₆R₂-2,7)}₂] [R = H, (Pr₄N)₂2a; R = t-Bu, (Pr₄N)₂2b, (Et₄N)₂2b; R = OMe, (Pr₄N)₂2c] wereprepared from PtCl₂, piperidine, the corresponding QCl salt, and 1a-c in molar ratio 1:2:2:2. In the absence ofQCl, the complexes (pipH)₂2b and [Pt(pip)₄]2b were isolated depending on the PtCl₂:pip molar ratio. The neutralcomplexes [Pt{S₂C=C(C₁₂H₆R₂-2,7)L₂] [L = PPh₃, R = H (3a), t-Bu (3b), OMe (3c); L = PEt₃, R = H (4a), t-Bu(4b), OMe (4c); L₂ = dbbpy, R = H (5a), t-Bu (5b), OMe (5c) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl)] weresimilarly prepared from the corresponding precursors [PtCl₂L₂] and 1a-c in the presence of piperidine. Oxidationof Q₂2b with [FeCp₂]PF₆ afforded the mixed Pt(II)-Pt(IV) complex Q₂[Pt₂{S₂C=C[C₁₂H₆(t-Bu)₂-2,7]}₄] (Q₂6, Q =Et₄N⁺, Pr₄N⁺). The protonation of (Pr₄N)₂2b with 2 equiv of triflic acid gave the neutral dithioato complex [Pt₂{S₂CCH[C₁₂H₆(t-Bu)₂-2,7]}₄] (7). The same reaction in 1:1 molar ratio gave the mixed dithiolato/dithioato complexPr₄N[Pt{S₂C=C[C₁₂H₆(t-Bu)₂-2,7]}{S₂CCH[C₁₂H₆(t-Bu)₂-2,7]}] (Pr₄N8) while the corresponding DMANH⁺ salt wasobtained by treating 7 with 2 equiv of 1,8-bis(dimethylamino)naphthalene (DMAN). The crystal structures of 3b and5c·CH₂Cl₂ have been solved by X-ray crystallography. All the platinum complexes are photoluminescent at 77 Kin CH₂Cl₂ or KBr matrix, except for Q₂6. Compounds 5a-c and Q8 show room-temperature luminescence in fluidsolution. The electronic absorption and emission spectra of the dithiolato complexes reveal charge-transfer absorptionand emission energies which are significantly lower than those of analogous platinum complexes with previouslydescribed 1,1-ethylenedithiolato ligands and in most cases compare well to those of 1,2-dithiolene complexes.