Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2024, Volume: 63, Number: 1, Pages: 369–380 Pages count : DOI: 10.1021/acs.inorgchem.3c03271

Authors

Afonin Mikhail Yu. ¹ , Martynenko Pavel A. ¹ , Kolybalov Dmitry S. ^1,2 , Khisamov Radmir M. ¹ , Konchenko Sergey N. ^1,2 , Sukhikh Taisiya S. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences
2	Department of Natural Sciences, National Research University - Novosibirsk State University

There is unceasing interest toward transformations of phosphine derivatives, which are facilitated by transition metals. We report a facile Pd(II)- and Pt(II)-assisted P–C bond cleavage in a luminescent 2-phenylbenzothiazole-based α-methylaminophosphine (PCN, 1). Specifically, reactions between 1 and [M(COD)Cl2] (M = Pd, Pt; COD = cycloocta-1,5-diene) in different solvents (methylene chloride, acetonitrile, pyridine, toluene) resulted in the formation of PPh2–, captured either as a bridging ligand in binuclear complexes with a {M2(PPh2)2} moiety or as an adduct to COD in [Pt2(PPh2COD)2Cl2]. The heterocyclic part transforms to annulated c-CN+ species with a 1,2-dihydroquinazoline cycle formed. In the presence of pyridine as a base, annulated form c-CN+ destabilizes and undergoes reverse cyclization transforming to deprotonated CN form. Quantum-chemical density functional theory (DFT) calculations predict that a crucial step in the reactions involves proton transfer from the N atom of the amino group of PCN to a neighboring molecule. A combination of high photophysical sensitivity of c-CN+ toward its immediate environment and rich structural capabilities in assembling (c-CN)22+ pairs in different crystal packings in a family of phases with the general formula (c-CN)2[M2(PPh2)2Cl4] allows one to fine-tune the luminescence properties of the latter. The results were rationalized as a variation of π–π intercationic spacings, which tunes the degree of excited-state charge transfer between c-CN+ cations. As a result, compounds with relatively short interplanar π–π-separation between the cations show a stronger charge-transfer-mediated bathochromic shift.

Afonin M.Y. , Martynenko P.A. , Kolybalov D.S. , Khisamov R.M. , Konchenko S.N. , Sukhikh T.S.
Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine
Inorganic Chemistry. 2024. V.63. N1. P.369–380. DOI: 10.1021/acs.inorgchem.3c03271 WOS Scopus РИНЦ OpenAlex

Submitted:	Sep 18, 2023
Accepted:	Nov 10, 2023
Published online:	Nov 21, 2023
Published print:	Jan 8, 2024

Web of science:	WOS:001138319200001
Scopus:	2-s2.0-85178569455
Elibrary:	64089671
OpenAlex:	W4388851851

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