Mono- and bis-(acetylacetonato) complexes of arene-ruthenium(II) and arene-osmium(II): variation of the binding mode of eta(1)-acetylacetonate with the nature of the arene

摘要

The mono(acetylacetonato) complexes [MCl(O,O'-acac)(eta (6)-arene)] (M = Ru, Os, arene = C6H6, 1,3,5-C6H3Me3, C6Me6; M = Os, arene = 1,2-C6H4Me2, 1,2,3-C6H3Me3), which are formed from [MCl2(eta (6)-arene)](2) and thallium or sodium acetylacetonate, react with thallium acetylacetonate to give bis(acetylacetonato) complexes [M(O,O'-acac)(eta (1)-acac)(eta (6)-arene)]. The eta (1)-acac ligand is bound through the gamma -carbon atom for M = Ru, Os, arene = C6H6; M = Os, arene = 1,2-C6H4Me2, 1,2,3-C6H3Me3 and through a keto-oxygen atom for M = Ru, Os, arene = 1,3,5-C6H3Me3, C6Me6, the difference being attributed to a combination of steric and electronic effects. Cationic ruthenium(II) derivatives [Ru(L)(O,O'-acac)(eta (6)-arene](+) (arene = C6H6, 1,3,5-C6H3Me3, C6Me6; L = DMSO, MeCN, py, PPh3) and [Ru(CO)(O,O'-acac)(eta (6)-arene](+) (arene = 1,3,5-C6H3Me3,C6Me6), and neutral osmium(II) eta (1)-acetato derivatives [Os(eta (1)-OAc)(O,O'-acac)(eta (6)-arene)] (arene = C6H6, 1,2-C6H4Me2, 1,2,3-C6H3Me3, 1,3,5-C6H3Me3, C6Me6) are also described. The molecular structures of the following complexes have been determined by X-ray crystallography: [Os(O,O'-acac)(eta (1)-C-acac)(eta (6)-1,2-C6H4Me2)], triclinic, space group P (1) over bar (No. 2), a = 9.922(2), b = 9.974(2), and c = 11.001(2) Angstrom, alpha = 68.33(1), beta = 64.18(1), and gamma = 62.38(1)degrees, V = 849.0(3) Angstrom (3), Z = 2; [Os(O,O'-acac)(eta (1)-O-acac)(eta (6)-1,3,5-C6H3Me3)], monoclinic, space group C2/c (No. 15), a = 16.032(4), b = 11.989(3), and c = 21.562(7) Angstrom, beta = 108.91(2)degrees, V = 3921(2) Angstrom, Z = 8; [Os(eta (1)-OAc)(O,O'-acac)(eta (6)-C6H6)], triclinic, space group P (1) over bar (No. 2), a = 8.368(4), b = 8.402(4), and c = 11.008(4) Angstrom, alpha = 71.68(3), beta = 69.35(3), and gamma = 69.77(3)degrees, V = 663.0(6) Angstrom (3), Z = 2. [References: 42]