Triphosphiranes as phosphinidene-transfer agents – synthesis of regular and chelating NHC phosphinidene adducts

Siewert, Jan-Erik; Schumann, André; Wellnitz, Tim; Dankert, Fabian; Hering-Junghans, Christian

doi:10.1039/d3dt02690f

Dalton Trans.

2023

DOI: 10.1039/d3dt02690f

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Triphosphiranes as phosphinidene-transfer agents – synthesis of regular and chelating NHC phosphinidene adducts

Jan-Erik Siewert,

André Schumann,

Tim Wellnitz

et al.

Abstract: In this contribution we describe the general use of aryl-substituted triphosphiranes (Ar3P3; Ar = Mes, Dip, Tip) as a phosphinidene transfer reagent towards N-Heterocyclic carbenes (NHCs) to give a library...

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2024

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Pd₈(PDip)₆: Cubic, Unsaturated, Zerovalent

Breitwieser,

Bevilacqua,

Mullassery

et al. 2024

Advanced Science

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Atomically precise nanoclusters hold promise for supramolecular assembly and (opto)electronic‐ as well as magnetic materials. Herein, this work reports that treating palladium(0) precursors with a triphosphirane affords strongly colored Pd8(PDip)6 that is fully characterized by mass spectrometry, heteronuclear and Cross‐Polarization Magic‐Angle Spinning (CP‐MAS) NMR‐, infrared (IR), UV–vis, and X‐ray photoelectron (XP) spectroscopies, single‐crystal X‐Ray diffraction (sc‐XRD), mass spectrometry, and cyclovoltammetry (CV). This coordinatively unsaturated 104‐electron Pd(0) cluster features a cubic Pd8‐core, µ4‐capping phosphinidene ligands, and is air‐stable. Quantum chemical calculations provide insight to the cluster's electronic structure and suggest 5s/4d orbital mixing as well as minor Pd─P covalency. Trapping experiments reveal that cluster growth proceeds via insertion of Pd(0) into the triphosphirane. The unsaturated cluster senses ethylene and binds isocyanides, which triggers the rearrangement to a tetrahedral structure with a reduced frontier orbital energy gap. These experiments demonstrate facile cluster manipulation and highlight non‐destructive cluster rearrangement as is required for supramolecular assembly.

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Pd₈(PDip)₆: Cubic, Unsaturated, Zerovalent

Breitwieser,

Bevilacqua,

Mullassery

et al. 2024

Advanced Science

Self Cite

View full text Add to dashboard Cite

show abstract

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Triphosphiranes as phosphinidene-transfer agents – synthesis of regular and chelating NHC phosphinidene adducts

Abstract: In this contribution we describe the general use of aryl-substituted triphosphiranes (Ar3P3; Ar = Mes, Dip, Tip) as a phosphinidene transfer reagent towards N-Heterocyclic carbenes (NHCs) to give a library...

Cited by 1 publication

References 57 publications

Pd₈(PDip)₆: Cubic, Unsaturated, Zerovalent

Pd₈(PDip)₆: Cubic, Unsaturated, Zerovalent

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Triphosphiranes as phosphinidene-transfer agents – synthesis of regular and chelating NHC phosphinidene adducts

Abstract: In this contribution we describe the general use of aryl-substituted triphosphiranes (Ar3P3; Ar = Mes, Dip, Tip) as a phosphinidene transfer reagent towards N-Heterocyclic carbenes (NHCs) to give a library...

Cited by 1 publication

References 57 publications

Pd8(PDip)6: Cubic, Unsaturated, Zerovalent

Pd8(PDip)6: Cubic, Unsaturated, Zerovalent

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Pd₈(PDip)₆: Cubic, Unsaturated, Zerovalent

Pd₈(PDip)₆: Cubic, Unsaturated, Zerovalent