The bimetallic activation of white phosphorus by trans-[RhCl(CO)(dppm)] 2 results in a Tetrahedro-Rh2P2 Moiety

Maria Caporali; Luca Gonsalvi; Vincenzo Mirabello; Andrea Ienco; Gabriele Manca; Fabrizio Zanobini; Maurizio Peruzzini

doi:10.1002/ejic.201400046

The bimetallic activation of white phosphorus by trans-[RhCl(CO)(dppm)] ₂ results in a Tetrahedro-Rh₂P₂ Moiety

Maria Caporali, Luca Gonsalvi, Vincenzo Mirabello, Andrea Ienco, Gabriele Manca, Fabrizio Zanobini, Maurizio Peruzzini

Department of Chemistry

Istituto di chimica dei composti organo metallici

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

10 Citations (SciVal)

Abstract

The reaction of trans-[RhCl(CO)(dppm)]₂ with P₄ carried out at room temperature showed that bimetallic cooperation resulted in the cleavage of P₄, giving a μ,η²-P₂ (μ-κ²:κ²-P₂) ligand coordinated to the two metal centres. The new complex cis-[Rh₂(CO) ₂(μ-dppm)₂(μ,η²-P₂)] has been fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The Rh-Rh distance of 2.723(18) Å is consistent with the presence of a metal-metal single bond, which was supported by theoretical analysis showing that the HOMO of the complex has metal-metal bond character. A literature survey revealed that, in most cases, the P ₂ unit acts as a P₂^4- ligand, and also in the case at hand the diphosphenyl ligand behaves as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations. The new complex cis-[Rh₂(CO)₂(μ-dppm) ₂(μ,η²-P₂)], obtained by activation of white phosphorus under mild conditions, was fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The P₂ unit acts as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations, as described by theoretical analysis. Copyright

Original language	English
Pages (from-to)	1652-1659
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	2014
Issue number	10
DOIs	https://doi.org/10.1002/ejic.201400046
Publication status	Published - 1 Apr 2014

Keywords

Metal-metal interactions
Phosphine ligands
Phosphorus
Rhodium

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10.1002/ejic.201400046

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title = "The bimetallic activation of white phosphorus by trans-[RhCl(CO)(dppm)] 2 results in a Tetrahedro-Rh2P2 Moiety",

abstract = "The reaction of trans-[RhCl(CO)(dppm)]2 with P4 carried out at room temperature showed that bimetallic cooperation resulted in the cleavage of P4, giving a μ,η2-P2 (μ-κ2:κ2-P2) ligand coordinated to the two metal centres. The new complex cis-[Rh2(CO) 2(μ-dppm)2(μ,η2-P2)] has been fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The Rh-Rh distance of 2.723(18) {\AA} is consistent with the presence of a metal-metal single bond, which was supported by theoretical analysis showing that the HOMO of the complex has metal-metal bond character. A literature survey revealed that, in most cases, the P 2 unit acts as a P24- ligand, and also in the case at hand the diphosphenyl ligand behaves as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations. The new complex cis-[Rh2(CO)2(μ-dppm) 2(μ,η2-P2)], obtained by activation of white phosphorus under mild conditions, was fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The P2 unit acts as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations, as described by theoretical analysis. Copyright ",

keywords = "Metal-metal interactions, Phosphine ligands, Phosphorus, Rhodium",

author = "Maria Caporali and Luca Gonsalvi and Vincenzo Mirabello and Andrea Ienco and Gabriele Manca and Fabrizio Zanobini and Maurizio Peruzzini",

year = "2014",

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T1 - The bimetallic activation of white phosphorus by trans-[RhCl(CO)(dppm)] 2 results in a Tetrahedro-Rh2P2 Moiety

AU - Caporali, Maria

AU - Gonsalvi, Luca

AU - Mirabello, Vincenzo

AU - Ienco, Andrea

AU - Manca, Gabriele

AU - Zanobini, Fabrizio

AU - Peruzzini, Maurizio

PY - 2014/4/1

Y1 - 2014/4/1

N2 - The reaction of trans-[RhCl(CO)(dppm)]2 with P4 carried out at room temperature showed that bimetallic cooperation resulted in the cleavage of P4, giving a μ,η2-P2 (μ-κ2:κ2-P2) ligand coordinated to the two metal centres. The new complex cis-[Rh2(CO) 2(μ-dppm)2(μ,η2-P2)] has been fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The Rh-Rh distance of 2.723(18) Å is consistent with the presence of a metal-metal single bond, which was supported by theoretical analysis showing that the HOMO of the complex has metal-metal bond character. A literature survey revealed that, in most cases, the P 2 unit acts as a P24- ligand, and also in the case at hand the diphosphenyl ligand behaves as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations. The new complex cis-[Rh2(CO)2(μ-dppm) 2(μ,η2-P2)], obtained by activation of white phosphorus under mild conditions, was fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The P2 unit acts as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations, as described by theoretical analysis. Copyright

AB - The reaction of trans-[RhCl(CO)(dppm)]2 with P4 carried out at room temperature showed that bimetallic cooperation resulted in the cleavage of P4, giving a μ,η2-P2 (μ-κ2:κ2-P2) ligand coordinated to the two metal centres. The new complex cis-[Rh2(CO) 2(μ-dppm)2(μ,η2-P2)] has been fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The Rh-Rh distance of 2.723(18) Å is consistent with the presence of a metal-metal single bond, which was supported by theoretical analysis showing that the HOMO of the complex has metal-metal bond character. A literature survey revealed that, in most cases, the P 2 unit acts as a P24- ligand, and also in the case at hand the diphosphenyl ligand behaves as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations. The new complex cis-[Rh2(CO)2(μ-dppm) 2(μ,η2-P2)], obtained by activation of white phosphorus under mild conditions, was fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The P2 unit acts as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations, as described by theoretical analysis. Copyright

KW - Metal-metal interactions

KW - Phosphine ligands

KW - Phosphorus

KW - Rhodium

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DO - 10.1002/ejic.201400046

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AN - SCOPUS:84904241354

SN - 1434-1948

VL - 2014

SP - 1652

EP - 1659

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 10

ER -

The bimetallic activation of white phosphorus by trans-[RhCl(CO)(dppm)] ₂ results in a Tetrahedro-Rh₂P₂ Moiety

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