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Alkali Metal Complexes of Phosphine-Borane-Substituted Benzyl Ligands and Their Application in the Synthesis of B-H···Sn Stabilized Dialkylstannylenes

Lookup NU author(s): Ahmed Alwaaly, Dr Casey Dixon, Dr Paul Waddell, Professor William Clegg, Professor Mike ProbertORCiD, Dr Ross Harrington, Dr Keith Izod

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


Abstract

© 2024 The Authors. Published by American Chemical Society.The benzyl-substituted phosphine-boranes PhCH2P(BH3)R2 [R = iPr (1H), Ph (2H), Cy (3H)] are accessible through either the reaction between R2PCl and PhCH2MgBr, followed by treatment with BH3·SMe2 or the reaction between R2P(BH)3Li and PhCH2Br. Treatment of 1H, 2H, or 3H with nBuLi, PhCH2Na, or PhCH2K gave the corresponding alkali metal complexes [{iPr2P(BH3)CHPh}Li(THF)]2 (1Li), [{Ph2P(BH3)CHPh}Li(OEt2)2] (2Li), [{Cy2P(BH3)CHPh}Li(TMEDA)] (3Li), [iPr2P(BH3)CHPh]Na (1Na), [{Ph2P(BH3)CHPh}Na(THF)2]2 (2Na), [Cy2P(BH3)CHPh]Na(THF)0.5 (3Na), [{iPr2P(BH3)CHPh}K]∞ (1K), [{Ph2P(BH3)CHPh}K(THF)]∞ (2K), and [{Cy2P(BH3)CHPh}K.0.5PhMe]∞ (3K). X-ray crystallography revealed that, while 2Li and 3Li crystallize as monomers, 1Li and 2Na crystallize as borane-bridged dimers. The potassium complexes 1K, 2K, and 3K all crystallize with polymeric structures, in which the monomer units are linked to each other through a range of both bridging BH3 groups and multihapto interactions between the potassium cations and the aromatic rings. The reactions between two equivalents of either 1Li or 3Li and Cp2Sn gave the corresponding dialkylstannylenes [{R2P(BH3)CHPh}2Sn] [R = iPr (1Sn), Cy (3Sn)]. These compounds were isolated as mixtures of the rac and meso diastereomers. X-ray crystallography reveals that rac-1Sn and rac-3Sn crystallize as discrete monomers each exhibiting two agostic-type B-H···Sn contacts.


Publication metadata

Author(s): Madlool AM, Alwaaly A, Dixon CM, Waddell PG, Clegg W, Probert MR, Harrington RW, Izod K

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2024

Volume: 43

Issue: 2

Pages: 164–173

Print publication date: 22/01/2024

Online publication date: 09/01/2024

Acceptance date: 20/12/2023

Date deposited: 30/01/2024

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society

URL: https://doi.org/10.1021/acs.organomet.3c00468

DOI: 10.1021/acs.organomet.3c00468


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Funding

Funder referenceFunder name
Ministry of Higher Education and Scientific Research, Iraq

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