Sodium phosphaethynolate as P-source for the synthesis of molecular rhodium phosphides: an exploratory study

Zhongshu Li; Jaap E. Borger; Thomas L. Gianetti; Fabian Müller; Bruno Pribanic; Peter Coburger; Hansjörg Grützmacher

doi:10.1039/d5dt02274f

Sodium phosphaethynolate as P-source for the synthesis of molecular rhodium phosphides: an exploratory study

Zhongshu Li
, Jaap E. Borger
, Thomas L. Gianetti
, Fabian Müller
, Bruno Pribanic
, Peter Coburger
, Hansjörg Grützmacher

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

Abstract

Molecular transition metal phosphides (TMPs) containing a Rh₂P₂ and unprecedented Rh₄P₄ core could be generated from Na[OCP] and rhodium(i) precursor complexes carrying the bischelating tropPPh₂ ligand. These reaction proceed through a formal P-transfer step (trop = 5H-dibenzo[a,d]cyclohepten-5-yl), which involves migration of the CO unit to the Rh(i) center. With the related tetradentate ligand trop₃P and tridentate ligand trop₂PPh the first neutral and anionic [Rh_x(L)_n(PCO)_y]_z complexes containing up to two rhodium centers and three intact phosphaethynolate units. These complexes are inert against CO migration. The results demonstrate a large influence of the metal coordination sphere on product formation, and indicate that low-coordinate rhodium(i) precursors are most effective for the preparation of RhP complexes using Na[OCP] as P-source.

Original language	English (US)
Journal	Dalton Transactions
DOIs	https://doi.org/10.1039/d5dt02274f
State	Accepted/In press - 2025
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

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10.1039/d5dt02274f

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title = "Sodium phosphaethynolate as P-source for the synthesis of molecular rhodium phosphides: an exploratory study",

abstract = "Molecular transition metal phosphides (TMPs) containing a Rh2P2 and unprecedented Rh4P4 core could be generated from Na[OCP] and rhodium(i) precursor complexes carrying the bischelating tropPPh2 ligand. These reaction proceed through a formal P-transfer step (trop = 5H-dibenzo[a,d]cyclohepten-5-yl), which involves migration of the CO unit to the Rh(i) center. With the related tetradentate ligand trop3P and tridentate ligand trop2PPh the first neutral and anionic [Rhx(L)n(PCO)y]z complexes containing up to two rhodium centers and three intact phosphaethynolate units. These complexes are inert against CO migration. The results demonstrate a large influence of the metal coordination sphere on product formation, and indicate that low-coordinate rhodium(i) precursors are most effective for the preparation of RhP complexes using Na[OCP] as P-source.",

author = "Zhongshu Li and Borger, \{Jaap E.\} and Gianetti, \{Thomas L.\} and Fabian M{\"u}ller and Bruno Pribanic and Peter Coburger and Hansj{\"o}rg Gr{\"u}tzmacher",

note = "Publisher Copyright: {\textcopyright} 2025 The Royal Society of Chemistry.",

year = "2025",

doi = "10.1039/d5dt02274f",

language = "English (US)",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - Sodium phosphaethynolate as P-source for the synthesis of molecular rhodium phosphides

T2 - an exploratory study

AU - Li, Zhongshu

AU - Borger, Jaap E.

AU - Gianetti, Thomas L.

AU - Müller, Fabian

AU - Pribanic, Bruno

AU - Coburger, Peter

AU - Grützmacher, Hansjörg

PY - 2025

Y1 - 2025

N2 - Molecular transition metal phosphides (TMPs) containing a Rh2P2 and unprecedented Rh4P4 core could be generated from Na[OCP] and rhodium(i) precursor complexes carrying the bischelating tropPPh2 ligand. These reaction proceed through a formal P-transfer step (trop = 5H-dibenzo[a,d]cyclohepten-5-yl), which involves migration of the CO unit to the Rh(i) center. With the related tetradentate ligand trop3P and tridentate ligand trop2PPh the first neutral and anionic [Rhx(L)n(PCO)y]z complexes containing up to two rhodium centers and three intact phosphaethynolate units. These complexes are inert against CO migration. The results demonstrate a large influence of the metal coordination sphere on product formation, and indicate that low-coordinate rhodium(i) precursors are most effective for the preparation of RhP complexes using Na[OCP] as P-source.

AB - Molecular transition metal phosphides (TMPs) containing a Rh2P2 and unprecedented Rh4P4 core could be generated from Na[OCP] and rhodium(i) precursor complexes carrying the bischelating tropPPh2 ligand. These reaction proceed through a formal P-transfer step (trop = 5H-dibenzo[a,d]cyclohepten-5-yl), which involves migration of the CO unit to the Rh(i) center. With the related tetradentate ligand trop3P and tridentate ligand trop2PPh the first neutral and anionic [Rhx(L)n(PCO)y]z complexes containing up to two rhodium centers and three intact phosphaethynolate units. These complexes are inert against CO migration. The results demonstrate a large influence of the metal coordination sphere on product formation, and indicate that low-coordinate rhodium(i) precursors are most effective for the preparation of RhP complexes using Na[OCP] as P-source.

UR - https://www.scopus.com/pages/publications/105018747019

UR - https://www.scopus.com/pages/publications/105018747019#tab=citedBy

U2 - 10.1039/d5dt02274f

DO - 10.1039/d5dt02274f

M3 - Article

AN - SCOPUS:105018747019

SN - 1477-9226

JO - Dalton Transactions

JF - Dalton Transactions

ER -

Sodium phosphaethynolate as P-source for the synthesis of molecular rhodium phosphides: an exploratory study

Abstract

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