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Organoplatinum Complexes of the N,N‐Diisopropyl‐diazabutadiene Ligand: A Structural and Spectroscopic Study
Author(s) -
Klein Axel,
Schurr Thilo,
Záliš Stanislav
Publication year - 2005
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200500106
Subject(s) - homo/lumo , ligand (biochemistry) , chemistry , molecular orbital , crystallography , quantum chemical , computational chemistry , stereochemistry , molecule , organic chemistry , biochemistry , receptor
Organoplatinum complexes [Pt(R) 2 (iPr‐DAB)], [PtCl(R)(iPr‐DAB)] or [PtCl 2 (iPr‐DAB)] (R = methyl or 2,4,6‐trimethylphenyl = mesityl, iPr‐DAB = N,N′‐diisopropyl‐1,4‐diazabutadiene) have been investigated by a combination of multiple spectroscopy (NMR, UV/VIS), single crystal XRD and quantum chemical calculations. Excellent agreement of calculated and experimental structural data from XRD or NMR provide a good basis for the quantum mechanical calculations. DFT calculations reveal the contributions of the DAB ligand and the co‐ligands to the electronic ground state. Methyl acts more or less purely as a σ‐donor, Cl or mesityl provide strong contributions (p or π) to the highest occupied molecular orbital (HOMO) whereas the lowest unoccupied molecular orbital (LUMO) is mainly centred to the DAB ligand. The TD‐DFT calculated electronic transitions were in excellent agreement with the experimental ones and allow reliable assignment of the absorption bands.