TY - JOUR
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
UR - http://www.scopus.com/inward/record.url?scp=84904241354&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1002/ejic.201400046
U2 - 10.1002/ejic.201400046
DO - 10.1002/ejic.201400046
M3 - Article
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 -