Platinum(II) and Palladium(II) Bis(chelate) Complexes Containing both Tri(1-cyclohepta-2, 4, 6-trienyl)phosphane, P(C₇H₇)₃, and Dichalcogenolato Ligands

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Herberhold, Max ; Schmalz, Thomas ; Milius, Wolfgang ; Wrackmeyer, Bernd:
Platinum(II) and Palladium(II) Bis(chelate) Complexes Containing both Tri(1-cyclohepta-2, 4, 6-trienyl)phosphane, P(C₇H₇)₃, and Dichalcogenolato Ligands.
In: Zeitschrift für anorganische und allgemeine Chemie. Bd. 628 (2002) Heft 5 . - S. 979-986.
ISSN 1521-3749
DOI: https://doi.org/10.1002/1521-3749(200206)628:5<979::AID-ZAAC979>3.0.CO;2-L

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Abstract

Tri(1-cyclohepta-2, 4, 6-trienyl)phosphane, P(C7H7)3 (P when coordinated to a metal atom), was used to stabilize complexes of platinum(II) and palladium(II) with chelating dichalcogenolato ligands as PM(E∩E) E = S, ∩ = CH2CH2, M = Pt (3a); E = S, ∩ = 1, 2-C6H4, M = Pt (5a), Pd (6a); E = S, ∩ = C(O)C(O), M = Pt (7a), Pd (8a); E = S, Se, ∩ = 1, 2-C2(B10H10), M = Pt (9a, 9b), Pd (10a, 10b); E = S, ∩ = Fe2(CO)6, M = Pt (11a), Pd (12a). Starting materials in all reactions were PMCl2 with M = Pt (1) and Pd (2). Attempts at the synthesis of PM(ER)2 with non-chelating chalcogenolato ligands were not successful. All new complexes were characterized by multinuclear magnetic resonance spectroscopy in solution (1H, 13C, 31P, 77Se and 195Pt NMR), and the molecular structures of 5a and 12a were determined by X-ray analysis. Both in the solid state and in solution the ligand P is linked to the metal atom by the P-M bond and by η2-C=C coordination of the central C=C bond of one of the C7H7 rings. In solution, intramolecular exchange between coordinated and non-coordinated C7H7 rings is observed, the exchange process being markedly faster in the case of M = Pd than for M = Pt.