Publication: Regioselective N- versus P-deprotonation of amino-phosphane tungsten(0) complexes
Authors
Terschüren, T. ; Junker, P. ; Schmer, A. ; Espinosa Ferao, A. F. ; Streubel, R.
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Publisher
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DOI
https://doi.org/10.3390/org3030013
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info:eu-repo/semantics/article
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© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).
This document is the Accepted version of a Published Work that appeared in final form in Organiscs . To access the final edited and published work see https://doi.org/10.3390/org3030013
Abstract
1,2-Bifunctional ligands are rare, in general, which holds especially for those with a P-N linkage. Herein, we report on the synthesis of P-tert-butyl substituted aminophosphane W(CO)5 complexes 3a–f (a: R = R’ = H; b: R = H, R = Me; c: R = H, R’ = ally; d: R = H, R’ = i-Pr; e: R = H, R’ = t-Bu; f: R = R’ = Me) obtained via formal N-H insertion reactions of Li/Cl phosphinidenoid complex 2 into NH bonds of ammonia and different amines. The 1,2-bifunctionality of 3b was addressed in targeted regioselective deprotonation reactions leading to amidophosphane complexes M-4b or M/N(H)Me phosphinidenoid complexes M-5b, respectively (M = Li, K). Remarkable was the observation that reactions of M-4b and M-5b with MeI as the electrophile resulted in the formation of the same product 7b. The constitution of all the compounds has been established by means of NMR and IR spectroscopy and mass spectrometry. Two possible reaction pathways were studied in detail using high-level DFT calculations
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Citation
Organics 2022, 3, 161–172.
https://www.mdpi.com/2673-401X/3/3/13/htm#
https://www.mdpi.com/2673-401X/3/3/13/htm#
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