以膦及咪唑配位基穩定鎳(III)－硫錯合物

Ni(III)-Thiolate Complexes Stabilized by Phosphine and Carbene Ligand

萬易承(Yi-Chen Wan)

指導教授 ： 廖文峯

國立清華大學/理學院/化學系/碩士(2013年)

摘要

摘要
將[PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)]與tris(1-pyrrolidinyl) phosphine (P(NC4H8)3)反應，合成出中性之[NiIII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (1)。並將其還原生成[PPN] [NiII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (2)。並由UV-Vis光譜儀、X-ray單晶繞射解析，鑑定化合物1及化合物2的結構。
將[PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)]或[NiIII(P(o-C6H3-3-SiMe3-2-S)3)]2與isocyanide (CNCy或CNtBu)反應，合成出中性之[NiIII(CNCy)(P(o-C6H3-3- SiMe3-2-S)3)]與[NiIII(CNtBu)(P(o-C6H3-3-SiMe3-2-S)3)]。並將其還原生成[PPN][NiII(CNCy)(P(o-C6H3-3-SiMe3-2-S)3)] (3)與[K-18-crown-6-ether][NiII(CNtBu) (P(o-C6H3-3-SiMe3-2-S)3)] (4)。並由UV-Vis光譜儀、IR光譜儀、電子順磁共振光譜儀、X-ray單晶繞射解析，鑑定其結構。
選擇低價數的Ni(0)做為活化小分子的金屬來源，以bipyridine為配位基，與CS2反應後，合成出[(bipy)NiII(η2-CS2)] (5)，並以Zn還原(bipy)NiII的方式，再與CS2反應亦可得到化合物5。

關鍵字

鎳(III)－硫錯合物

並列摘要

The stable nickel(III) complex [NiIII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (1) was isolated from the reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] and tris(1-pyrrolidinyl) phosphine (P(NC4H8)3). The stable nickel(II) complex [PPN] [NiII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (2) was obtained from reduction of Complex 1. Complex 1 and 2 were characterized by UV-vis and single-crystal X-ray diffraction.
The stable nickel(III) complexes [NiIII(CNCy)(P(o-C6H3-3-SiMe3-2-S)3)] and [NiIII(CNtBu)(P(o-C6H3-3-SiMe3-2-S)3)] were isolated from the reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] or [NiIII(P(o-C6H3-3-SiMe3-2-S)3)]2 and isocyanide (CNCy or CNtBu). The stable nickel(II) complex [PPN][NiII(CNCy) (P(o-C6H3-3-SiMe3-2-S)3)] (3) and [K-18-crown-6-ether][NiII(CNtBu)(P(o-C6H3-3- SiMe3-2-S)3)] (4) were synthesized by reducing NiIII-CNCy and NiIII-CNtBu. All these complexes were characterized by UV-vis, IR, EPR and single-crystal X-ray diffraction.
Using low valence Ni(0) as small molecule activactor, and bipyridine (bipy) as ligand to react with CS2, [(bipy)NiII(η2-CS2)] (5) can be successfully synthesized. Also, using (bipy)Ni0, reduced from (bipy)NiII species by Zn powder, react with CS2 to produce Complex 5.

並列關鍵字

Ni(III)-Thiolate Complexes

參考文獻

3. Jeoung, J.-H.; Dobbek, H. Science 2007, 131, 1461.

5. Calabrese, J. C.; Herskovitz, T.; Kinney, J. B. J. Am. Chem. Soc. 1983, 105, 5914.

6. Aresta, M.; Nobile, C. F. J. Chem. Soc. Chem. Commun. 1975, 636.

7. Bristow, G. S.; Hitchcock, P. B.; Lappert, M. F. J. Chem. Soc. Chem. Commun. 1981, 1145.

9. Tso, C. T.; Cutler, A. R. J. Am. Chem. Soc. 1986, 108, 6069.