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- Title
Correlations and Contrasts in Homo- and Heteroleptic Cyclic (Alkyl)(amino)carbene-Containing Pt<sup>0</sup> Complexes.
- Authors
Arnold, Nicole; Braunschweig, Holger; Brenner, Peter B.; Celik, Mehmet Ali; Dewhurst, Rian D.; Haehnel, Martin; Kramer, Thomas; Krummenacher, Ivo; Marder, Todd B.
- Abstract
An improved synthetic route to homoleptic complex [Pt(CAACMe)2] (CAAC=cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAACMe)(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 Pt0 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.
- Subjects
HOMOLEPTIC compounds; LINEAR free energy relationship; CARBENES; DENSITY functional theory; LEWIS pairs (Chemistry)
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 35, p12357
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201502048