Synthesis of a Tris(phosphaalkene)phosphine Ligand and Fundamental Organometallic Reactions on Its Sterically Shielded Metal Complexes

A new tris(phosphaalkene)phosphine ligand (1) was synthesized via phospha-Wittig methodology. Metalation of 1 with [RhCl(C2H4)2]2 and [IrCl(COE)2]2 (COE = cyclooctene) produced trigonal bipyramidal metal chlorides 2a (M = Rh) and 2b (M = Ir) in which the ligand coordinates in a tetradentate fash...

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Bibliographic Details
Published in:	Organometallics Vol. 35; no. 13; pp. 2224 - 2231
Main Authors:	Miura-Akagi, Preston M, Nakashige, Mika L, Maile, Caitlin K, Oshiro, Shelly M, Gurr, Joshua R, Yoshida, Wesley Y, Royappa, A. Timothy, Krause, Colleen E, Rheingold, Arnold L, Hughes, Russell P, Cain, Matthew F
Format:	Journal Article
Language:	English
Published:	American Chemical Society 11-07-2016
Online Access:	Get full text
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Summary:	A new tris(phosphaalkene)phosphine ligand (1) was synthesized via phospha-Wittig methodology. Metalation of 1 with [RhCl(C2H4)2]2 and [IrCl(COE)2]2 (COE = cyclooctene) produced trigonal bipyramidal metal chlorides 2a (M = Rh) and 2b (M = Ir) in which the ligand coordinates in a tetradentate fashion. X-ray crystallographic studies on 1·1.5THF, 2a·5CHCl3, and 2b·2.5CHCl3 combined with DFT calculations revealed a pronounced change in hybridization of the phosphaalkene phosphorus atoms upon coordination to the Rh/Ir centers, resulting in highly sterically congested metal complexes. Nucleophilic substitution on 2a with NaN3 afforded Rh–N3 complex 3; computational analysis, IR spectroscopy, and 15N{1H} NMR spectroscopy on isotopologue 15 N-3 provided additional structural insights. Halide abstraction of the chloride in 2b with AgOTf in the presence of acetonitrile afforded cationic Ir–NCMe complex 4. Evidence of the bound acetonitrile unit was obtained by 2D NMR spectroscopy and deuterium labeling studies.
ISSN:	0276-7333 1520-6041
DOI:	10.1021/acs.organomet.6b00250