C–H Activation of Pyrazolyl Ligands by Ru(II)

Joslin, Evan E.; Quillian, Brandon; Gunnoe, T. Brent; Cundari, Thomas R.; Sabat, Michal; Myers, William H.

doi:10.1021/ic500811n

Cited by 23 publications

(19 citation statements)

References 72 publications

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“…Therefore, the non‐innocence of Tp in this transformation and the observation of deuterium incorporation into the Tp 4‐positions provides indirect evidence for the generation of D + during the H/D exchange process. These results also demonstrates that the pyrazolyl rings of Tp and related ligands are not necessarily innocent in C–H activation processes, as has been observed by others …”

Section: Mechanistic Studies Of C–h Bond Activation By Tpr Complexessupporting

confidence: 86%

“…Based on published examples (and unpublished results from our lab), replacing the anionic Tp ligand of [TpRu(L)(NCMe)Ph] complexes with a charge‐neutral PPA ligand was estimated to shift the Ru(III/II) redox potentials positive by approximately 0.3 to 0.4 V (Figure ) , , . The complexes [(PPA)Ru(BPhos)(NCMe)Ph] + {PPA = tris(3,5‐dimethylpyrazolyl)methane; HC(pz*) 3 or tris(5‐methylpyrazolyl)methane; HC(pz 5‐Me ) 3 } were prepared to explore catalytic ethylene hydrophenylation .…”

Section: Catalytic C–h Bond Functionalization: Olefin Hydroarylationmentioning

confidence: 99%

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Transition Metal Mediated C–H Activation and Functionalization: The Role of Poly(pyrazolyl)borate and Poly(pyrazolyl)alkane Ligands

et al. 2016

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Section: Mechanistic Studies Of C–h Bond Activation By Tpr Complexessupporting

confidence: 86%

Section: Catalytic C–h Bond Functionalization: Olefin Hydroarylationmentioning

confidence: 99%

Transition Metal Mediated C–H Activation and Functionalization: The Role of Poly(pyrazolyl)borate and Poly(pyrazolyl)alkane Ligands

et al. 2016

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“…Since then isolation of different metal complexes with a wide range of structure and reactivity have been documented . These scorpionate ligands were extensively utilized as anionic σ‐donors and could coordinate most of the metals, including d‐ and f‐block elements of the Periodic Tableà, Many of the transition metal‐scorpionate complexes have found wide‐range of applications including enzyme mimicry, polymerizations, C–H activations, carbene, nitrene transfer reactions, aerobic oxidations, and a number of catalytic reactions . At a later stage, the sulfur donor analogues of pyrazolylborate ligands, namely hydro(trismethimazolyl)borate (Tm) was introduced by Reglinski .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structural Characterization, and Theoretical Studies of Silver(I) Complexes of Dihydrobis(2‐mercapto‐benzothiazolyl) Borate

Gomosta

Ramalakshmi

Arivazhagan

et al. 2019

Zeitschrift anorg allge chemie

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The complexes [Ag{κ 3 -S,SЈ,H-H 2 B(mbz) 2 }(PR 3 )] x , (1: x = 2, R = Ph; 2: x = 1, R = Cy) (mbz = 2-mercaptobenzothiazolyl) and amidine based dihydro(2-mercaptobenzo-thiazolyl) borates, [HN=C(Ph)-NH(R)-H 2 B(mbz)] (3: R = 2,6-diisopropylphenyl and 4: R = Ph) were synthesized and characterized by various spectroscopic methods and single-crystal X-ray crystallography. Complex [Ag{κ 3 -S,SЈ,H-H 2 B(mbz) 2 }(PPh 3 )] 2 (1) has a dimeric structure in its crystalline state, in which central silver(I) atoms adopt a * Prof. Dr. S. Ghosh E-Mail: sghosh@iitm.ac.in [a] 588 distorted trigonal bipyramid arrangement. In contrast, complex [Ag{κ 3 -S,SЈ,H-H 2 B(mbz) 2 }(PCy 3 )] (2) has a monomeric structure in its crystalline state, in which the central silver(I) atoms adopt a distorted trigonal planar arrangement. Infrared spectroscopy was utilized as a tool for investigating the presence of M···H-B interactions. In addition, density functional theory (DFT) calculations were used to analyse the B-H···[M] bonding interaction in the metal borate complexes. Crystal Data for 1: C 64 H 50 B 2 Ag 2 S 8 N 4 P 2 , M r = 1430.86, triclinic, P1, a = 11.5839(8) Å, b = 11.6836(8) Å, c = 12.2097(9) Å, α = 76.233(6)°, β = 80.921(6)°, γ = 73.582(6)°, V = 1532.3(2) Å 3 , Z = 1, ρ calcd. = 1.551 mg·m -3 , μ = 1.009 mm -1 , F(000) = 724, R 1 = 0.0507, wR 2 = 0.0653, 7252 independent reflections [2θ Յ 58.48°] and 378 parameters, Goodness-of-fit on F 2 = 1.029. Crystal Data for 2: C 32 H 43 BAgS 4 N 2 P, M r = 733.57, monoclinic, P2 1 /n, a = 9.7847(3) Å, b = 25.6692(6) Å, c = 13.9303(4) Å, α = 90°, β = 99.334(3)°, γ = 90°, V = 3452.48(17) Å 3 , Z = 4, ρ calcd. = 1.411 mg·m -3 , μ = 0.897 mm -1 , F(000) = 1520, R 1 = 0.0574, wR 2 = 0.0979, 8391 independent reflections [2θ Յ 58.066°] and 378 parameters, Goodness-of-fit on F 2 = 1.034. Crystal Data for 3: C 26 H 30 BS 2 N 3 , M r = 457.44, monoclinic, P2 1 /n, a = 12.8305(5) Å, b = 14.3085(4) Å, c = 13.9844(4) Å, α = 90°, β = 98.940(3)°, γ = 90°, V = 2536.14(14) Å 3 , Z = 4, ρ calcd. = 1.198 mg·m -3 , μ = 0.228 mm -1 , F(000) = 968, R 1 = 0.1074, wR 2 = 0.1880, 8484 independent reflections [2θ Յ 64.764°] and 310 parameters, Goodness-of-fit on F 2 = 1.106. Crystal Data for 4: C 20 H 18 BS 2 N 3 , M r = 585.61, monoclinic, P2 1 /c, a = 9.9343(10) Å, b = 14.2927(17) Å, c = 23.194(3) Å, α = 90°, β = 92.483(4)°, γ = 90°, V = 3290.2(6) Å 3 , Z = 4, ρ calcd. = 1.182 mg·m -3 , μ = 0.192 mm -593 independent reflections [2θ Յ 50.998°] and 447 parameters, Goodness-of-fit on F 2 = 1.032.Supporting Information (see footnote on the first page of this article): Detailed information about the packing diagram of compounds 3 and 4, spectroscopic data and DFT-computed results for compounds 1, 2, 3 and 4 have been provided in the supporting information.

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“…One strategy to access more electron‐deficient Ru(II) catalyst precursors has been to prepare cationic variants of TpRu(L)(NCMe)Ph complexes (Scheme ). Replacement of Tp with a tetra(pyrazolyl)alkane resulted in intramolecular C–H activation of a pyrazolyl ring . Thus, the cationic Ru(II) complex was synthesized using HC(pz 5 ) 3 (HC(pz 5 ) 3 =tris(5‐methyl‐pyrazolyl)methane) in which the pyrazolyl 5‐positions are protected by incorporation of methyl substituents.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Hydrophenylation of Ethylene Using a Cationic Ru(II) Catalyst: Styrene Production with Ethylene as the Oxidant

Jia

Gary

et al. 2017

Israel Journal of Chemistry

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The complex [(MeOTTM)Ru(P(OCH2)3CEt)(NCMe)Ph][BAr′4] (MeOTMM=4,4’,4’’‐(methoxymethanetriyl)‐tris(1‐benzyl‐1H‐1,2,3‐triazole), BAr′4=tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate) is used to catalyze the hydrophenylation of ethylene to produce styrene and ethylbenzene. The selectivity of styrene versus ethylbenzene varies as a function of ethylene pressure, and replacing the MeOTTM ligand with tris(1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)methanol reduces the selectivity toward styrene. For styrene production ethylene serves as the oxidant to produce ethane, as determined by both 1H NMR spectroscopy and GC‐MS. The Ru(III/II) potentials of [(MeOTTM)Ru[P(OCH2)3CEt](NCMe)Ph][BAr′4] (0.86 V) and [(HC(pz5)3)Ru[P(OCH2)3CEt](NCMe)Ph][BAr′4] (0.82 V) (HC(pz5)3=tris(5‐methyl‐pyrazolyl)methane) are nearly identical. Since catalytic conversion of ethylene and benzene by [(HC(pz5)3)Ru[P(OCH2)3CEt](NCMe)Ph][BAr′4] is known to selectively produce ethylbenzene, the formation of styrene using [(MeOTTM)Ru[P(OCH2)3CEt](NCMe)Ph][BAr′4] is attributed to the substituents on the triazole rings of the MeOTTM ligand.

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C–H Activation of Pyrazolyl Ligands by Ru(II)

Cited by 23 publications

References 72 publications

Transition Metal Mediated C–H Activation and Functionalization: The Role of Poly(pyrazolyl)borate and Poly(pyrazolyl)alkane Ligands

Transition Metal Mediated C–H Activation and Functionalization: The Role of Poly(pyrazolyl)borate and Poly(pyrazolyl)alkane Ligands

Synthesis, Structural Characterization, and Theoretical Studies of Silver(I) Complexes of Dihydrobis(2‐mercapto‐benzothiazolyl) Borate

Oxidative Hydrophenylation of Ethylene Using a Cationic Ru(II) Catalyst: Styrene Production with Ethylene as the Oxidant

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