Inorganic Chemistry, Vol.57, No.12, 6921-6931, 2018
Thiopyridazine-Based Palladium and Platinum Boratrane Complexes
Palladium and platinum boratrane complexes of the type [M{B(Pn(Me,tBu))(3)}(PPh3)] (M = Pd I, Pt 2b) have been prepared via the reaction of the soft scorpionate ligand potassium tris(4-methyl-6-tert-butyl-3-thiopyridazinyl)borate KTn(Me,tBu) 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(Me,tBu))3} (PPh3)H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br-2 and I-2 , respectively, led to the dihalide compounds of the molecular formula [M{B(Pn(Me,tBu))(3)}X-2] (3a,b-4a,b). Halide abstraction with Ag(SbF6) further gave interesting cationic compounds of either dimeric [Pd{B(Pn(Me,tBu))(3)}X(])2 (SbF6)(2) (5a,b) or monomeric [Pd{B(Pn(Me,tBu)}(NCMe)(2)](SbF6) (6) nature. All compounds were spectroscopically and Xray 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.