Mixed-Sandwich (Cp(HMB))Ru Complexes Containing Bis(methimazolyl)(pyrazolyl)borate (Cp* = eta(5)-C5Me5, HMB = eta(6)-C6Me6)

作者：Kuan Seah Ling; Leong Weng Kee^*; Webster Richard D; Goh Lai Yoong

来源：Organometallics, 2012, 31(14): 5159-5168.

DOI：10.1021/om300497p

Reaction of the scorpionate salt Li[HB(mt)(2)(pz)] (mt = N-methyl-2-mercaptoimidazol-1-yl, pz = pyrazolyl) with the organometallic complexes [Cp*RuOMe](2) (Cp* = eta(5)-C5Me5) (1) and [(HMB)RuCl2](2) (HMB = eta(6)-C6Me6) (2) gave the 18-electron Ru(II) complexes [Cp*Ru(kappa(3)-H,S,S%26apos;)-{HB(mt)(2)(pz)}] (3) and [(HMB)Ru(kappa(3)-H,S,S%26apos;)-{HB(mt)(2)(pz)}](4B)PF6 in moderate yields. In the absence of the PF6- anion, [(HMB)Ru(kappa(2)-S,S%26apos;-{HB(mt)(2)(pz)})(Cl)] [4C] was isolated as a coproduct with (4B)Cl. These complexes are the first examples of organoruthenium(II) complexes containing bis(methimazolyl)(pyrazolyl)borate ligands. Isomers of 4B were observed in solution, and the isomerization process was studied using variable-temperature H-1 NMR spectroscopy. The reactivity of 3 toward O-2 and CO was investigated, and in the process we isolated the first Ru(IV) peroxo complex containing a poly(methimazolyl)borate ligand, [Cp*Ru(kappa(2)-S,S%26apos;-{HB(mt)(2)(pz)})(eta(2)-O-2)] (5), and a CO adduct, [Cp*Ru(kappa(2)-S,S%26apos;-{HB(mt)(2)(pz)})(CO)] (6), respectively. The oxidation process was reversible, but treatment of 5 with CO converted it irreversibly to 6. All the new compounds were fully characterized, including by X-ray diffraction analyses. Cyclic voltammetric studies were also conducted for complexes 3, 5, and 6.

• 出版日期2012-7-23
• 单位南阳理工学院