Ruthenium, copper and ruthenium-copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand

Jingyun Wu; Michael A. Stevens; Michael G. Gardiner; Annie L. Colebatch

doi:10.1039/d4dt02755h

Ruthenium, copper and ruthenium-copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand

Jingyun Wu, Michael A. Stevens, Michael G. Gardiner, Annie L. Colebatch^*

^*Corresponding author for this work

The Australian National University

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

A new unsymmetrical dinucleating phosphino pyridyl 1,8-naphthyridine ligand PNNN is reported. Reaction with CuCl gave the dicopper complex [Cu₂(μ-Cl)₂(PNNN)] (1). In contrast, complexation of [RuCl₂(cymene)]₂ yielded a monometallic species [RuCl(cymene)(PNNN)]Cl ([2]Cl) in which the Ru is bound to the κ²-N,N, rather than κ²-P,N, binding pocket. The selective formation of the monoruthenium complex [2]Cl enabled synthesis of heterobimetallic complexes [RuCuCl₃(cymene)(PNNN)] (3) and [RuCuCl₂(cymene)(PNNN)]₂[PF₆]₂ ([4]2[PF6]2), which both exhibit κ¹-P coordination of Cu. Complexes 1 and [4]2[PF6]2 exhibit reversible dearomatisation-aromatisation behaviour at the metal-ligand cooperative methylene site upon sequential treatment with base (KO^tBu) and acid (HCl). Notably, deprotonation of [4]2[PF6]2 induces a shift in the coordination mode of Cu to κ²-P,N.

Original language	English
Journal	Dalton Transactions
DOIs	https://doi.org/10.1039/d4dt02755h
Publication status	Accepted/In press - 2024

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@article{38cc144915b54c52a92c2415e7bf17f5,

title = "Ruthenium, copper and ruthenium-copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand",

abstract = "A new unsymmetrical dinucleating phosphino pyridyl 1,8-naphthyridine ligand PNNN is reported. Reaction with CuCl gave the dicopper complex [Cu2(μ-Cl)2(PNNN)] (1). In contrast, complexation of [RuCl2(cymene)]2 yielded a monometallic species [RuCl(cymene)(PNNN)]Cl ([2]Cl) in which the Ru is bound to the κ2-N,N, rather than κ2-P,N, binding pocket. The selective formation of the monoruthenium complex [2]Cl enabled synthesis of heterobimetallic complexes [RuCuCl3(cymene)(PNNN)] (3) and [RuCuCl2(cymene)(PNNN)]2[PF6]2 ([4]2[PF6]2), which both exhibit κ1-P coordination of Cu. Complexes 1 and [4]2[PF6]2 exhibit reversible dearomatisation-aromatisation behaviour at the metal-ligand cooperative methylene site upon sequential treatment with base (KOtBu) and acid (HCl). Notably, deprotonation of [4]2[PF6]2 induces a shift in the coordination mode of Cu to κ2-P,N.",

author = "Jingyun Wu and Stevens, \{Michael A.\} and Gardiner, \{Michael G.\} and Colebatch, \{Annie L.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Royal Society of Chemistry.",

year = "2024",

doi = "10.1039/d4dt02755h",

language = "English",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - Ruthenium, copper and ruthenium-copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand

AU - Wu, Jingyun

AU - Stevens, Michael A.

AU - Gardiner, Michael G.

AU - Colebatch, Annie L.

PY - 2024

Y1 - 2024

N2 - A new unsymmetrical dinucleating phosphino pyridyl 1,8-naphthyridine ligand PNNN is reported. Reaction with CuCl gave the dicopper complex [Cu2(μ-Cl)2(PNNN)] (1). In contrast, complexation of [RuCl2(cymene)]2 yielded a monometallic species [RuCl(cymene)(PNNN)]Cl ([2]Cl) in which the Ru is bound to the κ2-N,N, rather than κ2-P,N, binding pocket. The selective formation of the monoruthenium complex [2]Cl enabled synthesis of heterobimetallic complexes [RuCuCl3(cymene)(PNNN)] (3) and [RuCuCl2(cymene)(PNNN)]2[PF6]2 ([4]2[PF6]2), which both exhibit κ1-P coordination of Cu. Complexes 1 and [4]2[PF6]2 exhibit reversible dearomatisation-aromatisation behaviour at the metal-ligand cooperative methylene site upon sequential treatment with base (KOtBu) and acid (HCl). Notably, deprotonation of [4]2[PF6]2 induces a shift in the coordination mode of Cu to κ2-P,N.

AB - A new unsymmetrical dinucleating phosphino pyridyl 1,8-naphthyridine ligand PNNN is reported. Reaction with CuCl gave the dicopper complex [Cu2(μ-Cl)2(PNNN)] (1). In contrast, complexation of [RuCl2(cymene)]2 yielded a monometallic species [RuCl(cymene)(PNNN)]Cl ([2]Cl) in which the Ru is bound to the κ2-N,N, rather than κ2-P,N, binding pocket. The selective formation of the monoruthenium complex [2]Cl enabled synthesis of heterobimetallic complexes [RuCuCl3(cymene)(PNNN)] (3) and [RuCuCl2(cymene)(PNNN)]2[PF6]2 ([4]2[PF6]2), which both exhibit κ1-P coordination of Cu. Complexes 1 and [4]2[PF6]2 exhibit reversible dearomatisation-aromatisation behaviour at the metal-ligand cooperative methylene site upon sequential treatment with base (KOtBu) and acid (HCl). Notably, deprotonation of [4]2[PF6]2 induces a shift in the coordination mode of Cu to κ2-P,N.

UR - https://www.scopus.com/pages/publications/85207296272

U2 - 10.1039/d4dt02755h

DO - 10.1039/d4dt02755h

M3 - Article

AN - SCOPUS:85207296272

SN - 1477-9226

JO - Dalton Transactions

JF - Dalton Transactions

ER -

Ruthenium, copper and ruthenium-copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand

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