Metal−Halide Bond Photoactivation from a Pt^III−Au^II Complex

Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates

“…9-11 While halide oxidation is typically the turnover-limiting step in HX-splitting photocatalysis. 12–14 the mechanism of photoreduction remains largely unknown. 15 …”

Diplatinum(III) [Cl2(μ2-amidinate)4] compound derived from air oxidation of mononuclear cis-[PtII(NH3)2(amidine-κ1)2]2+ complex

“…Among described Pt III species , di-and polynuclear complexes [2,[5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] bearing the homo Pt-Pt and the heteronuclear Pt-M (e.g., M = Au [6], Ru [7], Pd [8]) metal-metal bonds, are the most common. In the vast majority of cases, the metal-metal bond in these species is stabilized by O,O-(phosphates [19], sulphates [2], carboxylates [11,12,18]) O,N-(amidates [2,9,10,[14][15][16][17]23]), P,P-(pyrophosphites [2]), S,N-(pyrimidinthiolates, pyridinethiolates [2,19]), and S,S-(dithiocarboxylates [2]) bridging ligands.…”

“…1) [29]. The 1 H NMR spectrum in dmso-d 6 (2) has a lantern-type structure with four amidinate ligands bridging two Pt III centers (Fig. 1, Table 1).…”

Photocrystallographic Observation of Halide-Bridged Intermediates in Halogen Photoeliminations

“…These model structures are less severe truncations than have previously been employed in computational investigations of phosphazane bridged dirhodium complexes. 33−35 Gas-phase geometry optimizations and TD-DFT calculations were carried out using an SDD basis set for Rh 36 and 6-31G* for all other atoms. 37,38 Stationary points were characterized with frequency calculations.…”