286941-45-5Relevant academic research and scientific papers
Synthesis and reaction of ruthenium(II) complexes containing heteroatom donor (O, N, and P) tethered to η6-arene ring
Miyaki, Yoshiharu,Onishi, Takafumi,Kurosawa, Hideo
, p. 369 - 377 (2000)
Synthesis of ruthenium(II) complexes chelated by the η6-arene ring and a pendent donor atom (O, N, and P) is described. The alcohol-containing η6-arene ruthenium complexes [Ru{η6-C6H5(CH2)3OH}(PR3)Cl2] (1a R=Ph; lb R = Et) and [Ru{η6C6H5(CH2)3OH}L2Cl]BF4 (2a L22,2'-bipyridine; 2b L2= 1,10-phenanthroline; 2c L22,2-bis[4(R)-phenyl-1,3-oxazolon-2-yl]propane, (R)-bpop) were prepared by treatment of [Ru{η6-C6H5(CH2)3OH}Cl2]2 with tertiary phosphines or N,N'-chelate ligands/NaBF4, respectively. Addition of 1 equiv. of AgBF4 to a solution of complexes 1 or 2 gave alcohol chelate complexes [Ru{η6:η1-C6H5(CH2)3OH}(PR3)Cl]BF4 (3a-b) or [Ru{η6:η1-C6H5(CH2)3OH}L2](BF4)2 (4a-c), respectively. Although stable in MeOH, the alcohol-Ru chelate bond of 3 and 4 was cleaved by Cl(min) ion. Treatment of 4 with bases (OH(min), R3N) led to abstraction of the hydroxy proton to give alkoxy chelate complexes [Ru{η6:η1-C6H5(CH2)3O}L2]BF4 (5a-c). In CH2Cl2 acidity of the hydroxy proton in 4c was revealed to be comparable to that of N-methylbenzylammonium cation (pK(a) in H2O, ca. 11). Amino chelate complexes [Ru{η6:η1-C6H5(CH2)(n)NH2}(PPh3)Cl]BF4 (Tan = 3; 7b n = 2) were prepared by treatment of ammonium complexes [Ru{η6-C6H5(CH2)(n)NH3Cl}(PPh3)Cl2] (6a n = 3; 6b n = 2) with 1 equiv. of NaOH and NaBF4. 7 were stable to the attack of Cl(min) ion. In contrast, the similar treatment of dimethylammonium derivative [Ru{η6-C6H5(CH2)3NMe2HCl}(PPh3)Cl2] (8) with KOH gave a non-chelate complex [Ru{η6-C6H5(CH2)3NMe2}(PPh3)Cl2] (9). Phosphorous chelate complexes [Ru{η6:η1-C6H5(CH2)3OPPR2}Cl2] (10a R=Ph; 10b R=(i)Pr) were prepared by reaction of [Ru{η6C6H5(CH2)3OH}Cl2]2, PPR2Cl, and EtN(i)Pr2. Treatment of 10b with AgBF4 and CO (1 atm) gave the cationic carbonyl complex [Ru{η6:η1-C6H5(CH2)3OP(i)Pr2}(CO)Cl]BF4 (11). (C) 2000 Elsevier Science S.A.
