Synthesis and characterisation of a series of ruthenium scorpionate complexes with B–H  · · ·  M agostic interactions. Crystal structure of [RuH(κ2-N,BH TpTn)(PMe3)(cod)] (TpTn = hydrotris[3-(2-thienyl)pyrazol-1-yl]borate) † ‡

Caballero, Agustín; Torre, Felipe Gómez-de la; Jalón, Félix A.; Manzano, Blanca R.; Rodrı́guez, Ana; Trofimenko, Swiatoslaw; Sigalas, Michael P.

doi:10.1039/b008986i

Cited by 9 publications

(11 citation statements)

References 19 publications

(8 reference statements)

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“…Specifically, C−H bond activation is catalyzed by various (Tp)Ru(arene) complexes, 24 and complexes with agostic B−H to metal interactions have been reported. 4,25,26 Our work herein shows that 1,2,4-triazole-based scorpionate complexes are useful as base-free transfer hydrogenation catalysts, and they show new structural variations.…”

Section: Introductionmentioning

confidence: 74%

“…We report the first series of ruthenium scorpionate complexes based upon 1,2,4-triazole ligands of varied steric bulk. Scorpionate , complexes of ruthenium have most commonly been based upon pyrazole (in Tp − and related complexes and N,N,O complexes − ) but have also been reported with 1,2,3-triazole derivatives, other N donor heterocycles, and S donors. − Many of these complexes are promising catalysts or form interesting structures. Specifically, C–H bond activation is catalyzed by various (Tp)Ru(arene) complexes, and complexes with agostic B–H to metal interactions have been reported. ,, Our work herein shows that 1,2,4-triazole-based scorpionate complexes are useful as base-free transfer hydrogenation catalysts, and they show new structural variations.…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

et al. 2013

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The first ruthenium complexes of bulky tris(triazolyl)borate (Ttz) ligands were synthesized, fully characterized, and studied as transfer hydrogenation catalysts. The structures of the complexes were (η6-arene)RuCl(N,N), where in each case N,N is a κ2-Ttz or bis(triazolyl)borate (Btz) ligand (arene = p-cymene (1, 3, 5, 6), benzene (2), C6Me6 (4); N,N = TtzPh,Me* (1, 2), TtzMe,Me (3, 4), Ttz (5), Btz (6)). All but 5 were crystallographically characterized, and notably for 1 and 2 a rearranged ligand structure is observed (as indicated by an asterisk). These complexes were all effective catalysts for transfer hydrogenation of aryl ketones in isopropyl alcohol with base co-catalyst, with rates that were accelerated by moisture-free conditions. Complexes 1 and 2 are also effective catalysts for base-free transfer hydrogenation, and with 1 hydrogenation of several base-sensitive substrates was demonstrated. The ability of 1 to serve as a hydrogenation catalyst without base is attributed primarily to steric bulk, and a preliminary mechanism for formation of that active catalyst is proposed.

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Section: Introductionmentioning

confidence: 74%

Section: Introductionmentioning

confidence: 99%

Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

et al. 2013

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“…The absence of phenolic −OH resonance peak at 10.12 ppm in the ligand clearly indicates the formation of borate by the removal of hydrogen gas [38] and the presence of BH 2 signal at 0.72 ppm [39]. The other signals due to N=CH proton and aromatic ring proton appear at 7.99-7.97 and 7.55-6.52 ppm, respectively.…”

Section: Resultsmentioning

confidence: 99%

New Dihydro OO'Bis(Salicylidene) 2,2' Aminobenzothiazolyl Borate Complexes: Kinetic and Voltammetric Studies of Dimethyltin Copper Complex with Guanine, Adenine, and Calf Thymus DNA

Arjmand

Mohani

Parveen

2006

Bioinorganic Chemistry and Applications

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The newly synthesized ligand, dihydro bis(salicylidene) 2,2′ aminobenzothiazolyl borate (2), was derived from the reaction of Schiff base of 2-aminobenzothiazole and salicylaldehyde with KBH4. (3) and (4) complexes of (2) were synthesized and further metallated with dimethyltindichloride to yield heterobimetallic complexes (5) and (6). All complexes have been thoroughly characterized by elemental analysis, and IR, NMR, EPR, and UV-Vis spectroscopy and conductance measurements. The spectroscopic data support square planar environment around the atom, while the atom acquires pentacoordinate geometry. The interaction of complex (5) with guanine, adenine, and calf thymus DNA was studied by spectrophotometric, electrochemical, and kinetic methods. The absorption spectra of complex (5) exhibit a remarkable “hyperchromic effect” in the presence of guanine and calf thymus DNA. Indicative of strong binding of the complex to calf thymus DNA preferentially binds through position of guanine base, while the adenine shows binding to a lesser extent. The kinetic data were obtained from the rate constants, kobs, values under pseudo-first-order conditions. Cyclic voltammetry was employed to study the interaction of complex (5) with guanine, adenine, and calf thymus DNA. The CV of complex (5) in the absence and in the presence of guanine and calf thymus DNA altered drastically, with a positive shift in formal peak potential Epa and Epc values and a significant increase in peak current. The positive shift in formal potentials with increase in peak current favours strong interaction of complex (5) with calf thymus DNA. The net shift in E 1/2 has been used to estimate the ratio of equilibrium constants for the binding of and complexes to calf thymus DNA.

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“…3-Menthyl/Cl PAVMAA10 [22] 172 2.168(2) 2.026(5)-2.047(5) 118.1(2)-126.2(2) 3-Methylmenthyl/Cl YEYHAL [22] 297 2.158(2) 2.035(5)-2.040(5) 120.2(2)-125.0(2) 3-Mesityl/Cl TUHJEM [23] 120(2) 2.1400( 10 [a] /I LOQGOO [24] 150(2) 2.5607(7) 2.062(2) 122.16(7) 3-py,5-Me/I NEBKUA [25] r.t. 2.5059(4) 2.040(3)-2.122(3) 110.9(1)-132.23 (7) [a] Tp C * = tris[(3-methoxy-1,1-dimethyl)pyrazolyl]hydroborate.…”

Section: Structural Studiesmentioning

confidence: 99%

“…Photoluminescence studies were performed on [Tl(Tp Tn )] and compared with those on [Tl(Tp Ph )], [Tl(Tp Tol )], and [Tl(Tp tBu )]. [7] [Ir(Tp Tn )(olefin) 2 ] was prepared also, and its ability to activate C-H bonds was discussed by Carmona and co-workers, who reported also the reactivity of [Ir(Tp Tn )(butadiene)]. The reactivity of [RuH(Tp Tn )(cod)] towards L (L = PMe 3 , PMe 2 Ph, CNtBu) was investigated, and [RuH(κ 2 -N,BH-Tp Tn )(L)(cod)] complexes were obtained in which L replaced one of the coordinated N atoms to leave the BH···Ru interaction intact.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Crystal Structures of Scorpionate Complexes with the Hydrotris[3‐(2′‐thienyl)pyrazol‐1‐yl]borate Ligand

et al. 2014

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Six scorpionate complexes of group 10-12 metal elements (Cu I , Cu II , Zn II , and Cd II ) containing the anionic hydrotris[3-(2Ј-thienyl)pyrazol-1-yl]borate (Tp Tn ) ligand were prepared from the reaction of the thallium(I) salt of Tp Tn with the corresponding metal acceptors in chloroform solution. The air-and heat-stable complexes were characterized by analytical and spectroscopic methods (IR, conductivity, ESI-MS, 1 H NMR and 13 C NMR solution data) and structurally characterized by single-crystal X-ray studies. The Zn II complexes [Zn-(Tp Tn )X] (X = Cl or Br) contain a tripodal tridentate Tp Tn ligand, in which the tetrahedral metal environment is completed by a halide; in [Cd(Tp Tn ) 2 ], cadmium is found in an octahedral environment coordinated by two Tp Tn ligands. In [Cu(Tp Tn )(PPh 3 )]·CHCl 3 and [Cu(Tp Tn )(OC(O)CH 3 )], Tp Tn is also coordinated in the tripodal fashion, in which the copper environment is completed by a triphenylphosphine ligand in the former complex and by a symmetrically coordinated bi-[a]

show abstract

Synthesis and characterisation of a series of ruthenium scorpionate complexes with B–H · · · M agostic interactions. Crystal structure of [RuH(κ2-N,BH TpTn)(PMe3)(cod)] (TpTn = hydrotris[3-(2-thienyl)pyrazol-1-yl]borate) † ‡

Cited by 9 publications

References 19 publications

Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

New Dihydro OO'Bis(Salicylidene) 2,2' Aminobenzothiazolyl Borate Complexes: Kinetic and Voltammetric Studies of Dimethyltin Copper Complex with Guanine, Adenine, and Calf Thymus DNA

Synthesis, Characterization, and Crystal Structures of Scorpionate Complexes with the Hydrotris[3‐(2′‐thienyl)pyrazol‐1‐yl]borate Ligand

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