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Research Article Open access CC BY 4.0

Regioselective N- versus P-Deprotonation of Aminophosphane Tungsten(0) Complexes

Tatjana Terschüren, Philip Junker, Alexander Schmer, Arturo Espinosa Ferao, Rainer Streubel

Organics · pp. 161–172 · Published 22 Jun 2022

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.

Deprotonation Regioselectivity Chemistry Electrophile Bifunctional Medicinal chemistry Stereochemistry Nuclear magnetic resonance spectroscopy

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