- 作者: 陳建宏、王莉珺、廖文?
- 作者服務機構: Department of Chemistry, National Tsing Hua University, Hsinchu 30043, Taiwan, R.O.C.
- 中文摘要: Ruthenium-thiolate cyanocarbonyl compounds [Na·2THF][Ru(CO)(CN)(S-C5H4N)2] (2), and [PPN] [Ru(CO)(CN)(S-C5H4N)2] (3) were prepared from reactions of [Na][N(SiMe3)2] and cis-[Ru(CO)2(S-C5H4N)2] (1) obtained from reaction of Ru3(CO)12, Me3NO·2H2O, and 2-mercaptopyridine in THF. Complexes 1, 2 and 3 were characterized by IR and single-crystal X-ray diffraction. The IR spectrum of complex 2 in the aprotic solvent THF reveals two weak absorption bands for the CN- ligands at 2098 w and 2086 w cm-1 and one strong absorption band 1931 s cm-1 assigned to the carbonyl stretching frequency that support the dimeric architecture with two [Ru(CO)(CN)(S-C5H4N)2]- units connected through CN-Na+-NC interactions, as observed in the single-crystal X-ray structure. Ethylation of complex 3 by electrophile [Et3O][BF4] occurring initially at the more accessible, delicately balanced nucleophilic site to yield the charge-controlled, collision product 4 (Scheme II), and subsequently isomerizing to neutral [Ru(CO)(CNEt)(S-C5H4N)2] (5) demonstrated the enhanced nucleophilicity toward electrophiles with replacement of carbonyl ligand with cyanide ligand in complex 1, indicative of the strong s-donor role of the cyanide vs CO ligand. In comparison with displaying a reversible redox process of complex [Fe(CO)(CN)(S-C4H3N2)2]-, the electrochemistry of complex 3 reveals an irreversible oxidation at 0.29 V (vs Ag/AgNO3).
- 英文摘要: --
- 中文關鍵字: Ruthenium-thiolate cyanocarbonyl; Hydrogenase.
- 英文關鍵字: --