Tri(pyridylmethyl)phosphine: The Elusive Congener of TPA Shows Surprisingly Different Coordination Behavior

Autor:	Andrew J. P. White, Sandro Pagano, James D. Nobbs, Christopher J. Whiteoak, George J. P. Britovsek, Evgeny Kiryushchenkov
Rok vydání:	2013
Předmět:	Ligand field theory Ligand chemistry.chemical_element Photochemistry Medicinal chemistry Ruthenium Inorganic Chemistry Metal Chromium chemistry.chemical_compound chemistry visual_art visual_art.visual_art_medium Amine gas treating Physical and Theoretical Chemistry Acetonitrile Phosphine
Zdroj:	Inorganic Chemistry. 52:7000-7009
ISSN:	1520-510X 0020-1669
Popis:	Tri(pyridylmethyl)phosphine (TPPh), the remarkably elusive congener of tri(pyridylmethyl)amine (TPA), has been prepared, as well as the relative tri(N-methyl-pyridylamino)phosphine (TPAMP). The coordination properties of these new ligands have been evaluated for chromium(III), iron(II), and ruthenium(II) complexes and compared with the related TPA complexes. In all cases, a different coordination behavior has been observed whereby TPPh and TPAMP always act as tridentate ligands. A chromium(III) complex [Cr(TPPh)Cl3] has been prepared, which has shown low ethylene oligomerization activity. Octahedral low spin iron(II) complexes [Fe(TPPh)2](2+) and [Fe(TPAMP)2](2+) were obtained with two ligands bound to the metal center. Ruthenium(II) chloro complexes of TPA and TPPh undergo ligand exchange reactions in acetonitrile, and the ruthenium(II) complex [Ru(MeCN)2(TPA)](2+) can be oxidized by m-CPBA in acetonitrile to give a transient ruthenium(IV) oxo complex [Ru(O)(MeCN)(TPA)](2+). Attempts to generate high valent ruthenium(IV) oxo TPPh or TPAMP complexes could not be achieved, probably due to insufficient stabilization by these strong field ligands.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::01d93d9ad9db606e597b097934635f08 https://doi.org/10.1021/ic4005196 Zobrazit plný text záznamu