AI Article Synopsis
- An improved method for synthesizing the homoleptic complex [Pt(CAAC(Me))2] and new heteroleptic complexes [Pt(CAAC(Me))(PR3)] is discussed.
- Although the homoleptic complex is largely inert, one of the heteroleptic complexes shows reactivity through oxidative addition and metal-only Lewis pair formation.
- The study also compares the spectroscopic, structural, and electrochemical properties of the complexes, revealing notable differences in their reactivity despite similar structural characteristics.
Article Abstract
An improved synthetic route to homoleptic complex [Pt(CAAC(Me))2] (CAAC = cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAAC(Me))(PR3)] are presented. Although the homoleptic complex was found to be inert to many reagents, oxidative addition and metal-only Lewis pair (MOLP) formation was observed from one of the heteroleptic complexes. The spectroscopic, structural, and electrochemical properties of the zero-valent complexes were explored in concert with density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The homoleptic [Pt(CAAC)2] and heteroleptic [Pt(CAAC)(PR3)] complexes were found to be similar in their spectroscopic and structural properties, but their electrochemical behavior and reactivity differ greatly. The unusually strong color of the CAAC-containing Pt(0) complexes was investigated by TD-DFT calculations and attributed to excitations into the LUMOs of the complexes, which are predominantly composed of bonding π interactions between Pt and the CAAC carbon atoms.
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| http://dx.doi.org/10.1002/chem.201502048 | DOI Listing |
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