Tri(pyridylmethyl)phosphine : the elusive congener of TPA shows surprisingly different coordination behavior

WHITEOAK, Christopher, NOBBS, James D., KIRYUSHCHENKOV, Evgeny, PAGANO, Sandro, WHITE, Andrew J.P. and BRITOVSEK, George J.P. (2013). Tri(pyridylmethyl)phosphine : the elusive congener of TPA shows surprisingly different coordination behavior. Inorganic Chemistry, 52 (12), 7000-7009.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic4005196
Link to published version:: 10.1021/ic4005196

Abstract

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.

Item Type: Article
Identification Number: 10.1021/ic4005196
Depositing User: Christopher Whiteoak
Date Deposited: 01 Apr 2016 11:11
Last Modified: 01 Apr 2016 11:11
URI: http://shura.shu.ac.uk/id/eprint/11781

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