TY - JOUR
T1 - PSb+P Ligand
T2 - Platform for a Stibenium to Transition-Metal Interaction
AU - Srungavruksham, Nagarjuna Kumar
AU - Liu, Yi Hung
AU - Tsai, Ming Kang
AU - Chiu, Ching Wen
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/4/6
Y1 - 2020/4/6
N2 - The coordination chemistry of cationic divalent pnictogen ligands, such as nitrenium and phosphenium, has been well-explored in recent years. However, corresponding studies of a heavier congener, stibenium ion, are rare. To better facilitate a Sb+-metal interaction, a tridentate P-Sb+-P ligand with two phosphine buttresses was designed and synthesized, and its coordination chemistry toward late transition metals was investigated. The stibenium ligand was delivered as an activated P(SbCl)P-AgOTf complex (2) that releases AgCl and the P-Sb+-P ligand upon the treatment with transition metals. Reacting 2 with Rh(I) and Ir(I) metals yielded the anticipated stibenium-transition-metal complexes [(Rh(COD)Cl)2(μ-PSb+P)] OTf ([3][OTf]) and [(Ir(COD)Cl)2(μ-PSb+P)] OTf ([4][OTf]). The M-Sb+-M bridging structure was confirmed by single-crystal X-ray crystallography, and the bonding situation was examined computationally. Theoretical studies revealed the presence of three-center delocalized M-Sb+-M bonding interactions in [3][OTf] and [4][OTf].
AB - The coordination chemistry of cationic divalent pnictogen ligands, such as nitrenium and phosphenium, has been well-explored in recent years. However, corresponding studies of a heavier congener, stibenium ion, are rare. To better facilitate a Sb+-metal interaction, a tridentate P-Sb+-P ligand with two phosphine buttresses was designed and synthesized, and its coordination chemistry toward late transition metals was investigated. The stibenium ligand was delivered as an activated P(SbCl)P-AgOTf complex (2) that releases AgCl and the P-Sb+-P ligand upon the treatment with transition metals. Reacting 2 with Rh(I) and Ir(I) metals yielded the anticipated stibenium-transition-metal complexes [(Rh(COD)Cl)2(μ-PSb+P)] OTf ([3][OTf]) and [(Ir(COD)Cl)2(μ-PSb+P)] OTf ([4][OTf]). The M-Sb+-M bridging structure was confirmed by single-crystal X-ray crystallography, and the bonding situation was examined computationally. Theoretical studies revealed the presence of three-center delocalized M-Sb+-M bonding interactions in [3][OTf] and [4][OTf].
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U2 - 10.1021/acs.inorgchem.9b03530
DO - 10.1021/acs.inorgchem.9b03530
M3 - Article
C2 - 32193926
AN - SCOPUS:85082194499
SN - 0020-1669
VL - 59
SP - 4468
EP - 4474
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 7
ER -