Trismethimazolylhydroborate (Tm) complexes of ruthenium and manganese

Synthesis, characterization, and catalytic activity of half‐sandwich ruthenium complexes with pyridine/phenylene bridged NHC = E (NHC = N‐heterocyclic carbene, E = S, Se) ligands

“…The average Ru–S distance is 2.3934 Å, which is longer than in the corresponding half‐sandwich ruthenium complex with borate‐centered tridentate NHC=S ligand [Cp*Ru III {HB(mt) 3 }]Cl (mt = N ‐methyl‐2‐mercaptoimidazol‐1‐yl, mean S–Ru = 2.3756 Å) [ 31 ] and shorter than those found in the corresponding complex containing the Tm ligand [Ru( p ‐cymene)(Tm)]Cl (Tm = trismethimazolylhydroborate, mean S–Ru = 2.411 Å). [ 61 ] However, the average C = S distance (1.694 Å) is shorter than in [Cp*Ru III {HB (mt) 3 }]Cl (mean C–S = 1.723 Å) and [Ru( p ‐cymene)(Tm)]Cl (mean C–S = 1.723 Å). As shown in Figure , complexes 1b and 1c have isostructure.…”

Soft Scorpionate Ligands Based on Imidazole‐2‐thione Donors

“…Group 7: A range of complexes of form [Mn(R′Tm R )(CO) 3 ] have been prepared from [Mn(NCMe) 3 (CO) 3 ]PF 6 by Bailey (Tm Me )97 and [Mn(CO) 5 Br] by Rabinovich (Tm t Bu , Tm Bz , Tm p Tol , PhTm Me ) 41. These have facially capping κ 3 ‐S,S,S ligands, while the related Bm R complexes have κ 3 ‐S,S,H ligands, with rather short M ··· H–B distances, They illustrate once more, via the C–O stretching frequencies, that the magnitude of the electron donation from the Tm ligands is somewhat greater than in either the Tp or Cp analogues.…”

Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

“…98 Instead, the reaction of 8 with 1 equiv of the tripodal ligand sodium tris-(methimazolyl)hydroborate (NaTm, Chart 30) at ambient temperature afforded fac-Ru(Tm)Cl(dmso-S) 2 in low yield, in which Tm is coordinated through the three sulfur atoms. 311 The reaction of 8 with 1 equiv of the N 2 O chelate 6-carboxy-2,2′-bipyridine (6-carboxy-bpy) in refluxing aqueous methanol yielded, after deprotonation, [RuCl(dmso) 2 (6-carboxylato-bpy)], while the reaction with 2 equiv of the ligand in the presence of NEt 3 afforded the homoleptic complex [Ru(6-carboxylato-bpy) 2 ], in which each anionic chelate has a meridional coordination geometry. 168 Treatment of 8 with 2 equiv of the N 3 tridentate chelating isoindoline ligand 1,3-bis-(2-(4-methylpyridyl)imino)isoindoline (bpsndH, Chart 30) in a basic alcoholic solution afforded the bis-(isoindolinato) complex Ru(bpsnd) 2 , which bears two deprotonated tridentate ligands.…”

“…312 Similarly, the reaction of 8 with an excess of the bridging bistridentate chelating ligand 1,3,5,7-tetrakis(2-(4-secbutylpyridyl)imino)benzopyrrole (HL-LH, Chart 30) in basic dioxane yielded the (HL-L)Ru(L-LH) complex, further exploited for the construction of a trinuclear Ru(II) species. 311 2 complex, which was characterized also through X-ray crystallography. 316 The reaction of 8 with the square-planar tetradentate N 2 O 2 ligand 6,6′-bis(benzoylamino)-2,2′-bipyridine (H 2 babp, Chart 30) in the presence of NaH gave trans-Ru(babp)(dmso) 2 ; 317 one of the two dmso ligands, whose coordination mode was not addressed, was easily replaced by heterocyclic N-donors (L) to yield trans-Ru(babp)(dmso)(L) complexes.…”