Aryl C(sp(2))–X Coupling (X = C, N, O, Cl) and Facile Control of N-Mono- and N,N-Diarylation of Primary Alkylamines at a Pt(IV) Center

[Image: see text] We present the first example of an unprecedented and fast aryl C(sp(2))–X reductive elimination from a series of isolated Pt(IV) aryl complexes (Ar = p-FC(6)H(4)) LPt(IV)F(py)(Ar)X (X = CN, Cl, 4-OC(6)H(4)NO(2)) and LPt(IV)F(2)(Ar)(HX) (X = NHAlk; Alk = n-Bu, PhCH(2), cyclo-C(6)H(11), t-Bu, cyclopropylmethyl) bearing a bulky bidentate 2-[bis(adamant-1-yl)phosphino]phenoxide ligand (L). The C(sp(2))–X reductive elimination reactions of all isolated Pt(IV) complexes follow first-order kinetics and were modeled using density functional theory (DFT) calculations. When a difluoro complex LPt(IV)F(2)(Ar)(py) is treated with TMS–X (TMS = trimethylsilyl; X= NMe(2), SPh, OPh, CCPh) it also gives the corresponding products of the Ar–X coupling but without observable LPt(IV)F(py)(Ar)X intermediates. Remarkably, the LPt(IV)F(2)(Ar)(HX) complexes with alkylamine ligands (HX = NH(2)Alk) form selectively either mono- (ArNHAlk) or diarylated (Ar(2)NAlk) products in the presence or absence of an added Et(3)N, respectively. This method allows for a one-pot preparation of diarylalkylamine bearing different aryl groups. These findings were also applied in unprecedented mono- and di-N-arylation of amino acid derivatives (lysine and tryptophan) under very mild conditions.