On the Nature of “RuCl(dmso)₂{HB(mt)₃}” (mt = methimazolyl)

Abstract

The high-yield product of the reaction of [RuCl 2 (dmso) 4 ] (dmso ) dimethylsulfoxide) with Na[HB(mt) 3 ] (mt ) methimazolyl) is not, as reported, the complex [RuCl(dmso) 2 {κ 3 -S,S′,S′′-HB(mt) 3 }] but rather the isomeric [RuCl(dmso) 2 {κ 3 -H,S,S′-HB(mt) 3 }], which features a three-center, two-electron B-H-Ru interaction, as also found for the complex [RuH(PPh 3 ) 2 {κ 3 -H,S,S′-H 2 B(mt) 2 }], which results from [RuHCl(PPh 3 ) 3 ] and Na[H 2 B(mt) 2 ].

Strong agostic-type interactions in ruthenium benzylidene complexes containing 7-azaindole based scorpionate ligands

“…11 B{ 1 H}-NMR and 11 B-NMR spectra were referenced externally relative to BF 3 ·OEt 2 . 31 16 were charged in a Schlenk tube. This was connected to a Schlenk line and THF (approximately 15 mL) was added at room temperature to give a deep green solution.…”

“…This was placed in the freezer (-30 • C) to give 4 as an olive-green microcrystalline solid, which was isolated by filtration, washed with 2 ¥ 3 mL n-pentane and dried under vacuum. Yield: 42 mg (34% 102.68, 103.02, 103.49, 114.68, 115.33, 116.52, 122.11, 122.37, 122.55, 124.33, 128.03, 128.46, 128.71 (appears in the DEPT-135), 129.62, 130.33, 130.44, 130.59, 132.31, 140.88, 142.33, 142.81, 153.53, 154.50, 155.19 (aromatics), 320.3 (detected indirectly by a gc2hsqcse experiment, [Ru]=C(H)Ph) (the ipso carbon in [Ru]=C(H)C 6 H 5 could not be located); 31 10b were charged in a Schlenk tube. This was connected to a Schlenk line and DCM (approx.…”

Synthetic reactions and coordination modes of ruthenium complexes with tris(mercaptomethimazolyl)borate ligands

“…However, this simple analogy failed in the previous reports to prepare organometallic derivatives of the Tm R ligand [16][17][18]. Recently, Hill and co-workers have successfully reported this class of complexes to include examples based on osmium, rhodium, iridium, and platinum [19][20][21][22][23][24][25][26][27][28], while further examples based on iron, cobalt, rhodium, iridium, nickel, and palladium have been provided by the groups of Rabinovich [29], Tatsumi [11], Parkin [30][31][32] [17,18,35], and [RuH (CO)(PPh 3 )(Tm Me )] and [RuCl(dmso) 2 (Tm Me )] with a j 3 -H,S,S-Ru coordination mode [16,28], presumably bidentate coordination of Tm Me via two of its three sulfur donor atoms, which reveals an agostic BAHARu interaction [16,28]. We describe in this paper the [28,36], expand the pool of ruthenium-sulfur complexes with now available for the comparative study of their molecular structures and spectroscopic properties.…”

Synthesis and characterization of ruthenium hydride and halide complexes with bis(2-mercapto-1-arylimidazolyl)borate ligands

“…The infrared spectra of 1e6 include absorptions of both BeHeRu (around 2200 cm À1 ) [27] and terminal BeH (about 2410 cm À1 ) [24] stretches. The very strong absorption around 1950 cm À1 could be ascribed to CO group in 1e6.…”