Journal
INORGANIC CHEMISTRY
Volume 61, Issue 33, Pages 13007-13014Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c01132
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Funding
- SERB, New Delhi [ECR/2016/000733, SPG/2021/003237]
- IISER Tirupati
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By synthesizing and characterizing a series of novel cAAC-anchored boryl-and stibanyl-phosphaalkenes, it has been found that these compounds exhibit redox noninnocent behavior in solution, while revealing their molecular structures and properties.
Cyclic alkyl(amino) carbene (cAAC)-anchored boryl-and stibanyl-phosphaalkenes with general formula cAAC = P-ER2 [E = B, R = (NiPr2)(2) (3a-c); E = Sb, R = 2,4,6-triisopropylphenyl (5a-b)] have been synthesized and utilized as precursors for the bis-phosphaalkenyl dichlorogermane [(cAAC = P)(2)GeCl2] (6) and the first molecular example of a neutral polymeric mixed-valence Ag-I/Ag-II phosphinidenide complex [(cAACP)(2)(Ag4AgCl4)-Ag-I-Cl-II](n) (7). All compounds have been characterized by single-crystal X-ray diffraction and further investigated by nuclear magnetic resonance (NMR), mass spectrometric analysis, and UV-vis/fluorescence measurements. The paramagnetic complex 7 has been characterized by ESR spectroscopy. Cyclic voltammetry studies of compounds 3/5 have suggested possible one-electron quasi-reversible reductions, indicating their redox noninnocent behavior in solution. Quantum chemical studies revealed the electron-sharing nature of the P-B and P-Sb sigma bonds in compounds 3 and 5, and the polar CcAAC = P bonds in compounds 3, 5, and 6 prevailing their phosphaalkene structures over phosphinidenes.
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