One‐Step Synthesis of a Platinum(0)–Gallium(III) Chrysene Complex

Abstract

Recent investigations of gallium(iii) halide-aromatic solvent systems with respect to platinum-group metal halides have shown them to be very efficient reducing media. [1, 2] Another attractive feature of gallium(iii) halides is their aptitude to abstract halide ions from other metal halides, which facilitates metal-metal bond formation. Taking advantage of these properties, we have prepared and crystallographically characterized a series of dipalladium(i) and diplatinum(i) complexes [M 2 (h 6 -arene) 2 (GaX 4 ) 2 ] (arene = benzene, its alkylated derivatives, or naphthalene; X = Cl À or Br À ). [1, 2]

Mononuclear η6‐Arene Complexes of Lanthanides: One‐Step Syntheses, Crystal Structures, and Arene Exchange

“…In addition, GaX 3 -arene solutions display a high reducing ability, [18][19][20] and one may anticipate the formation of lanthanide complexes with a formal oxidation state that is lower than +3. In practice, even the use of an excess of GaX 3 and heating of the reaction mixture leads to the Ln III complexes in all cases.…”

“…Thus, a series of low-valent platinum(0), platinum(I), and palladium(I) complexes supported by direct metal-metal bonds was isolated and crystallographically characterized. [18][19][20] In these reactions gallium(III) halides not only act as acceptors of the halide atoms, but also facilitate the process of reduction of the transition-metal halides, probably via an oxidation of the arenes. The present study has been performed in order to extend this synthetic approach to the chemistry of the f-block elements.…”

Noble metals

“…220 A one-step synthesis of a Pt(0)-Ga(II) chrysene complex [Pt 2 Ga 2 Cl 2 (m-Cl) 2 (chrysene) 4 ](Ga 3 Cl 10 ) has also been described. 221 Detailed electrochemical studies on the oxidation of the half-lantern [Pt 2 -(k 2 -As,C-L) 2 (m-As,C-L) 2 ] and full-lantern [Pt 2 (m-As,C-L) 4 ] [L = C 6 H 3 -5-Me-2-AsPh 2 ] complexes reveal the presence of an exceptionally stable dinuclear {Pt 2 } 21 and evidence to support the conclusion that the unpaired electron is distributed equally between the two Pt atoms. 222 Finally, a mixture of the cis and trans isomers of [Pt(PPh 3 ) 2 (SeCC-n-C 5 H 11 ) 2 ]) has been shown to slowly isomerize to the trans form; the coordination geometry from cis to trans induces significant changes in the spectroscopic parameters, which do not comply with the previously anticipated donor-acceptor properties of selenolate ligands.…”