Reactions of ruthenium(II) with thiamacrocycles: structures of trans-dichlorido-1,4,7,10,13,16-hexathiacyclooctadecane-ruthenium(II), bis-(dichloro-dimethylsulfoxide-ruthenium(II)) 1,4,7,10,13-pentathiacyclopentadecane, and cis-dichlorido-1,4,8,11-tetrathiacyclotetradecane-ruthenium(II)

摘要

The straightforward reaction of thiamacrocycles (1,4,7,10,13,16-hexathiacyclooctadecane ([18]aneS(6)), 1,4,7,10,13-pentathiacyclopentadecane ([15]aneS(5)), 1,4,8,11-tetrathiacyclotetradecane ([14]aneS(4)), and 1,4,7-trithiacyclononane ([9]aneS(3))) with RuCl2(dmso)(4) in CHCl3 or CH2Cl2 has produced several crystalline compounds which have been structurally characterized. X-ray crystallographic analysis reveals the following complexes: [trans-RuCl2([18]aneS(6))] (1), [(RuCl2(dmso))(2)[15]aneS(5)] (2), [cis-RuCl2([14]aneS(4))] (3), and [RuCl2([9]aneS(3))(dmso)] (4). As anticipated all low-spin Ru(II) ions have distorted octahedral environment. Unforeseen was the formation of a dinuclear compound, with one sulfur atom of [15]aneS(5) forming a bridge between two cis-RuCl2 moieties. For all these structures, the Ru-S separations range from 2.29 to 2.36 (thiaether) with much larger values for Ru-S-Ru bridge (2.509 (3) and 2.499 (3) ), and 2.24-2.25 (dimethyl sulfoxide). The crystallographic parameters at - 100 A degrees C are as follows: 1: monoclinic, space group P2(1)/c; a, b, c (): 8.8975 (3), 11.9747 (5), 9.5666 (4); beta = 109.923 (1)A degrees. V = 958.27 (7) (3), Z = 2; 2: monoclinic, space group P2(1)/c; a, b, c (): 23.029 (5), 8.3909 (19), 14.220 (3); beta = 102.118 (6)A degrees. V = 2686.6 (10) (3), Z = 4; 3: monoclinic, space group P2(1)/n; a, b, c (): 8.5071 (12), 14.272 (2), 12.9361 (18), beta = 93.566 (4)A degrees. V = 1567.6 (4) (3), Z = 4; 4: monoclinic, space group P2(1)/c; a, b, c (): 8.2424 (5), 12.4688 (7), 14.8408 (10), beta = 104.546 (2). V = 1476.34 (16) (3), Z = 4 (the last structure is practically identical to already measured at different temperature).