Attempted Syntheses of ZnPhos-Ruthenium Complexes (ZnPhos = bis(2-(diphenylphosphinophenyl)zinc)

Amber Walsh; Lewis Ludovic; John Lowe; Mary Mahon; Michael Whittlesey

doi:10.1039/D5DT01160D

Attempted Syntheses of ZnPhos-Ruthenium Complexes (ZnPhos = bis(2-(diphenylphosphinophenyl)zinc)

Amber Walsh, Lewis Ludovic, John Lowe, Mary Mahon, Michael Whittlesey

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

Abstract

Efforts to prepare Ru-ZnPhos complexes (ZnPhos = bis(2-diphenylphosphinophenyl)zinc) through in situ reactions of the bis-cyclometallated phosphine RuZn ₂ complex [Ru(PPh ₃)(C ₆H ₄PPh ₂) ₂(ZnMe) ₂] (1) with the N-Et and N- ⁱPr substituted N-heterocyclic carbenes IEt ₂Me ₂ (1,3-diethyl-4,5-dimethylimidazol-2-ylidene) and I ⁱPr ₂Me ₂ (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) gave instead the cycloruthenated/cyclozincated bimetallic species [Ru(IEt ₂Me ₂′)(C ₆H ₄PPh ₂)(PPh ₂(C ₆H ₄)Zn{IEt ₂Me ₂})H] (5; IEt ₂Me ₂′ = cyclometallated IEt ₂Me ₂) and [Ru(PPh ₃)(C ₆H ₄PPh ₂)(PPh(C ₆H ₄) ₂Zn{I ⁱPr ₂Me ₂})H] (7) respectively, both of which feature new Zn-NHC bonds. An alternative approach involving substitution of free ZnPhos into ruthenium monodentate phosphine precursors proved marginally more successful. Heating [Ru(PPh ₃) ₃(CO)H ₂] with excess ZnPhos gave a tetrametallic species 13 comprised of a Ru centre coordinated to ZnPhos and two ZnC ₆H ₄PPh ₂ ligands formed via Zn-C cleavage of two ZnPhos ligands. Substitution into the NHC analogue [Ru(PPh ₃) ₂(IMe ₄)(CO)H ₂] (IMe ₄ = 1,3,4,5-tetramethylimidazol-2-ylidene) was successful and generated the bridging dihydride complex [Ru(ZnPhos)(IMe ₄)(CO)(μ-H) ₂] (14).

Original language	English
Pages (from-to)	11371-11381
Number of pages	11
Journal	Dalton Transactions
Volume	54
Issue number	29
Early online date	3 Jul 2025
DOIs	https://doi.org/10.1039/D5DT01160D
Publication status	Published - 22 Jul 2025

Data Availability Statement

The data supporting this article have been included as part of the ESI.† Crystallographic data for 9, 10, 11, 7, 13, and 14 have been deposited at the CCDC under accession numbers 2409552, 2409553, 2409554, 2409555, 2409556 and 2409557† and can be obtained from https://www.ccdc.cam.ac.uk/.

Acknowledgements

We thank Dr Robin Stein (Bruker) for solid-state NMR assistance and Dr David Liptrot for use of his ATR-IR spectrometer. We dedicate this paper to Professor Paul Pringle, on the occasion of his upcoming retirement, in recognition of his many contributions to the chemistry of metal-phosphine complexes.

Funding

The work was supported by an EPSRC Doctoral Training Award to AMW. We thank Dr Robin Stein (Bruker) for solid-state NMR assistance and Dr David Liptrot for use of his ATR-IR spectrometer. We dedicate this paper to Professor Paul Pringle, on the occasion of his upcoming retirement, in recognition of his many contributions to the chemistry of metal-phosphine complexes.

Funders	Funder number
Engineering and Physical Sciences Research Council

ASJC Scopus subject areas

Inorganic Chemistry

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@article{91c07ea4736149858303b81ee5fc0757,

title = "Attempted Syntheses of ZnPhos-Ruthenium Complexes (ZnPhos = bis(2-(diphenylphosphinophenyl)zinc)",

abstract = "Efforts to prepare Ru-ZnPhos complexes (ZnPhos = bis(2-diphenylphosphinophenyl)zinc) through in situ reactions of the bis-cyclometallated phosphine RuZn 2 complex [Ru(PPh 3)(C 6H 4PPh 2) 2(ZnMe) 2] (1) with the N-Et and N- iPr substituted N-heterocyclic carbenes IEt 2Me 2 (1,3-diethyl-4,5-dimethylimidazol-2-ylidene) and I iPr 2Me 2 (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) gave instead the cycloruthenated/cyclozincated bimetallic species [Ru(IEt 2Me 2′)(C 6H 4PPh 2)(PPh 2(C 6H 4)Zn\{IEt 2Me 2\})H] (5; IEt 2Me 2′ = cyclometallated IEt 2Me 2) and [Ru(PPh 3)(C 6H 4PPh 2)(PPh(C 6H 4) 2Zn\{I iPr 2Me 2\})H] (7) respectively, both of which feature new Zn-NHC bonds. An alternative approach involving substitution of free ZnPhos into ruthenium monodentate phosphine precursors proved marginally more successful. Heating [Ru(PPh 3) 3(CO)H 2] with excess ZnPhos gave a tetrametallic species 13 comprised of a Ru centre coordinated to ZnPhos and two ZnC 6H 4PPh 2 ligands formed via Zn-C cleavage of two ZnPhos ligands. Substitution into the NHC analogue [Ru(PPh 3) 2(IMe 4)(CO)H 2] (IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene) was successful and generated the bridging dihydride complex [Ru(ZnPhos)(IMe 4)(CO)(μ-H) 2] (14).",

author = "Amber Walsh and Lewis Ludovic and John Lowe and Mary Mahon and Michael Whittlesey",

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T1 - Attempted Syntheses of ZnPhos-Ruthenium Complexes (ZnPhos = bis(2-(diphenylphosphinophenyl)zinc)

AU - Walsh, Amber

AU - Ludovic, Lewis

AU - Lowe, John

AU - Mahon, Mary

AU - Whittlesey, Michael

PY - 2025/7/22

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N2 - Efforts to prepare Ru-ZnPhos complexes (ZnPhos = bis(2-diphenylphosphinophenyl)zinc) through in situ reactions of the bis-cyclometallated phosphine RuZn 2 complex [Ru(PPh 3)(C 6H 4PPh 2) 2(ZnMe) 2] (1) with the N-Et and N- iPr substituted N-heterocyclic carbenes IEt 2Me 2 (1,3-diethyl-4,5-dimethylimidazol-2-ylidene) and I iPr 2Me 2 (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) gave instead the cycloruthenated/cyclozincated bimetallic species [Ru(IEt 2Me 2′)(C 6H 4PPh 2)(PPh 2(C 6H 4)Zn{IEt 2Me 2})H] (5; IEt 2Me 2′ = cyclometallated IEt 2Me 2) and [Ru(PPh 3)(C 6H 4PPh 2)(PPh(C 6H 4) 2Zn{I iPr 2Me 2})H] (7) respectively, both of which feature new Zn-NHC bonds. An alternative approach involving substitution of free ZnPhos into ruthenium monodentate phosphine precursors proved marginally more successful. Heating [Ru(PPh 3) 3(CO)H 2] with excess ZnPhos gave a tetrametallic species 13 comprised of a Ru centre coordinated to ZnPhos and two ZnC 6H 4PPh 2 ligands formed via Zn-C cleavage of two ZnPhos ligands. Substitution into the NHC analogue [Ru(PPh 3) 2(IMe 4)(CO)H 2] (IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene) was successful and generated the bridging dihydride complex [Ru(ZnPhos)(IMe 4)(CO)(μ-H) 2] (14).

AB - Efforts to prepare Ru-ZnPhos complexes (ZnPhos = bis(2-diphenylphosphinophenyl)zinc) through in situ reactions of the bis-cyclometallated phosphine RuZn 2 complex [Ru(PPh 3)(C 6H 4PPh 2) 2(ZnMe) 2] (1) with the N-Et and N- iPr substituted N-heterocyclic carbenes IEt 2Me 2 (1,3-diethyl-4,5-dimethylimidazol-2-ylidene) and I iPr 2Me 2 (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) gave instead the cycloruthenated/cyclozincated bimetallic species [Ru(IEt 2Me 2′)(C 6H 4PPh 2)(PPh 2(C 6H 4)Zn{IEt 2Me 2})H] (5; IEt 2Me 2′ = cyclometallated IEt 2Me 2) and [Ru(PPh 3)(C 6H 4PPh 2)(PPh(C 6H 4) 2Zn{I iPr 2Me 2})H] (7) respectively, both of which feature new Zn-NHC bonds. An alternative approach involving substitution of free ZnPhos into ruthenium monodentate phosphine precursors proved marginally more successful. Heating [Ru(PPh 3) 3(CO)H 2] with excess ZnPhos gave a tetrametallic species 13 comprised of a Ru centre coordinated to ZnPhos and two ZnC 6H 4PPh 2 ligands formed via Zn-C cleavage of two ZnPhos ligands. Substitution into the NHC analogue [Ru(PPh 3) 2(IMe 4)(CO)H 2] (IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene) was successful and generated the bridging dihydride complex [Ru(ZnPhos)(IMe 4)(CO)(μ-H) 2] (14).

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U2 - 10.1039/D5DT01160D

DO - 10.1039/D5DT01160D

M3 - Article

SN - 1477-9226

VL - 54

SP - 11371

EP - 11381

JO - Dalton Transactions

JF - Dalton Transactions

IS - 29

ER -

Attempted Syntheses of ZnPhos-Ruthenium Complexes (ZnPhos = bis(2-(diphenylphosphinophenyl)zinc)

Abstract

Data Availability Statement

Acknowledgements

Funding

ASJC Scopus subject areas

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