TY - JOUR
T1 - Phosphonium Ylides vs Iminophosphoranes
T2 - The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes
AU - Popovici, Ingrid
AU - Barthes, Cécile
AU - Tannoux, Thibault
AU - Duhayon, Carine
AU - Casaretto, Nicolas
AU - Monari, Antonio
AU - Auffrant, Audrey
AU - Canac, Yves
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/2/6
Y1 - 2023/2/6
N2 - The coordinating properties of two families of ylides, namely, phosphonium ylides and iminophosphoranes, differently substituted at the ylidic center (CH2− vs NiPr−), have been investigated in structurally related cationic phosphine-ylide Rh(CO)2 complexes obtained from readily available phosphine-phosphonium salt precursors derived from an ortho-phenylene bridge. However, while the Rh(CO)2 complex bearing the P+−CH2− donor moiety proved to be stable, the P=NiPr donor end appeared to induce lability to one of the CO groups. All of the RhI carbonyl complexes in both ylide series were fully characterized, including through X-ray diffraction analysis. Based on the experimental and calculated infrared (IR) CO stretching frequencies in Rh(CO)2 complexes, we evidenced that the phosphonium ylide ligand is a stronger donor than the iminophosphorane ligand. However, we also found that the difference in the intrinsic electronic properties can be largely compensated by the introduction of an iPr substituent on the N atom of the iminophosphorane, hence pointing to the noninnocent role of the peripheral substituent and opening novel possibilities to tune the properties of metal complexes containing ylide ligands.
AB - The coordinating properties of two families of ylides, namely, phosphonium ylides and iminophosphoranes, differently substituted at the ylidic center (CH2− vs NiPr−), have been investigated in structurally related cationic phosphine-ylide Rh(CO)2 complexes obtained from readily available phosphine-phosphonium salt precursors derived from an ortho-phenylene bridge. However, while the Rh(CO)2 complex bearing the P+−CH2− donor moiety proved to be stable, the P=NiPr donor end appeared to induce lability to one of the CO groups. All of the RhI carbonyl complexes in both ylide series were fully characterized, including through X-ray diffraction analysis. Based on the experimental and calculated infrared (IR) CO stretching frequencies in Rh(CO)2 complexes, we evidenced that the phosphonium ylide ligand is a stronger donor than the iminophosphorane ligand. However, we also found that the difference in the intrinsic electronic properties can be largely compensated by the introduction of an iPr substituent on the N atom of the iminophosphorane, hence pointing to the noninnocent role of the peripheral substituent and opening novel possibilities to tune the properties of metal complexes containing ylide ligands.
U2 - 10.1021/acs.inorgchem.2c04151
DO - 10.1021/acs.inorgchem.2c04151
M3 - Article
C2 - 36704899
AN - SCOPUS:85147171727
SN - 0020-1669
VL - 62
SP - 2376
EP - 2388
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -