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

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

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

Author(s) -

Evan E. Joslin,

Brandon Quillian,

T. Brent Gunnoe,

Thomas R. Cundari,

Michal Sabat,

William H. Myers

Publication year - 2014

Publication title -

inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.348

H-Index - 233

eISSN - 1520-510X

pISSN - 0020-1669

DOI - 10.1021/ic500811n

Subject(s) - chemistry , aryl , intramolecular force , ligand (biochemistry) , medicinal chemistry , ring (chemistry) , stereochemistry , ruthenium , yield (engineering) , alkyl , trifluoromethyl , receptor , catalysis , organic chemistry , biochemistry , materials science , metallurgy

Previously, hydridotris(pyrazolyl)borate (Tp) Ru(II) alkyl and aryl complexes of the type TpRu(L)(NCMe)R (R = methyl or aryl; L = charge-neutral two-electron donating ligand) were demonstrated to activate aromatic C-H bonds. To determine the impact of replacing the anionic Tp ligand with charge-neutral poly(pyrazolyl)alkane ligands, [(C(pz)4)Ru(P(OCH2)3CEt)(NCMe)Me][BAr'4] (pz = pyrazolyl, BAr'4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) was prepared. Heating a C6D6 solution of [(C(pz)4)Ru(P(OCH2)3CEt)(NCMe)Me][BAr'4] with 1 equiv of NCMe resulted in C-H activation of the 5-position of a pyrazolyl ring to yield [(κ(3)-(N,C(5),N)C(pz)4)Ru(P(OCH2)3CEt)(NCMe)2][BAr'4] and CH4. Intramolecular C-H activation of the 5-position of a pyrazolyl ring also occurred when (η(6)-p-cymene)Ru(P(OCH2)3CEt)(Br)Ph was heated in the presence of C(pz)4 to yield [(κ(3)-N,C(5),N)C(pz)4]Ru(P(OCH2)3CEt)(NCMe)Br and C6H6. Density functional theory calculations revealed that the different reactivities of TpRu(P(OCH2)3CEt)(NCMe)R and [(C(pz)4)Ru(P(OCH2)3CEt)(NCMe)Me][BAr'4] result from the stronger binding of the Tp pyrazolyl rings to Ru(II) compared to that of C(pz)4.

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