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Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.

Authors :: Holler S
Tüchler M
Steller BG
Belaj F
Veiros LF
Kirchner K
Mösch-Zanetti NC
Source :: Inorganic chemistry [Inorg Chem] 2018 Jun 18; Vol. 57 (12), pp. 6921-6931. Date of Electronic Publication: 2018 Jun 07.
Publication Year :: 2018
Abstract: Palladium and platinum boratrane complexes of the type [M{B(Pn <superscript>Me, tBu</superscript> ) <subscript>3</subscript> }(PPh <subscript>3</subscript> )] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft scorpionate ligand potassium tris(4-methyl-6- tert-butyl-3-thiopyridazinyl)borate KTn <superscript>Me, tBu</superscript> with bis(triphenylphosphine)metal(II) dichloride. While reaction with the Pd precursor allowed direct isolation of a symmetric boratrane complex, the Pt analogue led to the hydrido compound [Pt{B(Pn <superscript>Me, tBu</superscript> ) <subscript>3</subscript> }(PPh <subscript>3</subscript> )H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br <subscript>2</subscript> and I <subscript>2</subscript> , respectively, led to the dihalide compounds of the molecular formula [M{B(Pn <superscript>Me, tBu</superscript> ) <subscript>3</subscript> }X <subscript>2</subscript> ] (3a,b-4a,b). Halide abstraction with Ag(SbF <subscript>6</subscript> ) further gave interesting cationic compounds of either dimeric [Pd{B(Pn <superscript>Me, tBu</superscript> ) <subscript>3</subscript> }X] <subscript>2</subscript> (SbF <subscript>6</subscript> ) <subscript>2</subscript> (5a,b) or monomeric [Pd{B(Pn <superscript>Me, tBu</superscript> ) <subscript>3</subscript> }(NCMe) <subscript>2</subscript> ](SbF <subscript>6</subscript> ) (6) nature. All compounds were spectroscopically and X-ray crystallographically characterized revealing strong metal to boron interactions. DFT calculations of 1, 2a, and 2b confirm the strong M-B interaction and a high positive charge on the metal centers.