具三甲基矽基之磷硫多牙基的新穎三價銅錯合物合成及其性質探討

Synthesis and Structure of Novel Copper(III) Complexes with a Supporting Polydentate Ligand of Tris(3-(trimethylsilyl)2-mercaptophenyl)phosphine and their Property Study

林宗翰

指導教授 ： 李位仁

國立臺灣師範大學/理學院/化學系/碩士(2011年)

摘要

我們利用去質子化的三腳四牙配位基P(C6H3-3-SiMe3-2-SH)3 (PS3TMS)與CuCl2和PPNCl在乙腈與四氫呋喃混合溶劑下反應，會發生自身氧化還原反應得到[PPN][CuClPS3TMS] (1)和PPNCuCl2，利用通入氧氣來氧化正二價銅離子可提高錯合物1的產率。如果使用類似之去質子化配位基PS3進行反應，就沒有辦法觀察到正三價銅錯合物之產生。
將錯合物1和NaOMe進行反應會得到Cu(NHPPh3)PS3TMS (3)，因此推測反應過程中可能是先經由β-hydride elimination生成[PPN] [CuHPS3TMS]的中間態，進而與[PPN]+反應生成NHPPh3並配位到正三價銅離子中心，才會得到錯合物3。為了證明此反應過程會經過[PPN][CuHPS3TMS]中間態，因此將錯合物1直接與KBEt3H反應，也成功地得到錯合物3。若將錯合物1的陽離子置換成[PPh4]+生成[PPh4] [CuClPS3TMS] (2)，再與KBEt3H反應，會得到K2[(CuPS3TMS)2] (4)和氫氣，這個結果告訴我們反應過程中可能生成[PPh4][CuHPS3TMS]。

關鍵字

銅三價 ； 四牙基 ； 磷硫多牙基 ； 金屬錯合物

並列摘要

The tripodal tetradentate ligand P(C6H3-3-SiMe3-2-SH)3 (PS3TMSH3) was deprotonated by NaH, and further reacted with CuCl2 in CH3CN and THF. The disproportionation of CuCl2 was occurred to form [PPN][CuClPS3TMS] (1) and PPNCuCl2. The yield of complex 1 in previous reaction could be improved by using dry O2 to oxidize Cu(II) ion. A similar ligand, P(C6H4- 2-SH)3 (PS3H3) was also employed to reacted with CuCl2. However, no CuIII complex was observed.
Reaction of 1 with NaOMe afforded complex, [Cu(NHPPh3)PS3TMS] (3). This results suggested that an intermediates, [PPN][CuHPS3TMS], was generated through β-hydride elimination. The hydride attacted the cation, [PPN]+, to form NHPPh3, which coordinated to the CuIII center. To prove the formation of the [PPN][CuHPS3TMS] intermediates, complex 1 was reacted with KBEt3H to afford complex 3. If the counter ion of 1 changed to [PPh4]+ to form [PPh4][CuClPS3TMS] (2). Reaction of 2 with KBEt3H gave a new dinuclear complex, K2[(CuPS3TMS)2] (4) and H2 suggesting the possibility of [PPh4][CuHPS3TMS] formation.

參考文獻

14. Tzung-Wen Chiou and Wen-Feng Liaw Inorg. Chem. 2008, 47, 7908-7913.

11. Debabrata Maiti, Julia S. Woertink, Amy A. Narducci Sarjeant, Edward I. Solomon and Kenneth D. Karlin Inorg. Chem. 2008, 47, 3787-3800.

10. Stephen W. Ragsdale and Manoj Kumar Chem. Rev. 1996, 96, 2515-2539.

3. Christopher Federsel, Albert Boddien, Ralf Jackstell, Reiko Jennerjahn, Paul J. Dyson, Rosario Scopelliti, Gabor Laurenczy, and Matthias Beller Angew. Chem. Int. Ed. 2010, 49, 9777 –9780.

8. Robert R. Eady Coordination Chemistry Reviews 2003, 237, 23-30.