Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]^VI Complex

Abstract

As part of our interest in the photochemistry of platinum/p-block element complexes, we now report on the synthesis and photoreduction of [(Ph)((o-Ph 2 P)C 6 H 4 ) 2 GePtCl 3 ] (2-Ph), a complex featuring a tetravalent platinum center connected to a germyl ligand. When in the presence of a chlorine trap, 2-Ph undergoes a clean photolysis that affords [(Ph)((o-Ph 2 P)C 6 H 4 ) 2 GePtCl] (1-Ph) and [(Cl)((o-Ph 2 P)C 6 H 4 ) 2 GePtCl](1-Cl) as confirmed by NMR spectroscopy. While the formation of 1-Ph results from the elimination of a chlorine equivalent from 2-Ph, the formation of 1-Cl indicates chlorobenzene elimination, which was confirmed and quantified using GC-MS. These results provide a unique example of a germanium-centered light-induced reduction process resulting in the ipso-chlorination of a phenylgermanium species.

Tetrelanes versus Tetrylenes as Precursors to Transition Metal Complexes Featuring Tridentate PEP Tetryl Ligands (E=Si, Ge, Sn)

“…While the former gave the rhodium(I) dicarbonyl derivative [Rh(PSi Me P G )(CO) 2 ], the latter afforded a rhodium(III) complex, [RhHCl(PSi Me P G )]. [63] All PGeP tridentate germyl complexes that have thus far been prepared from metal-free germanes have used germanes of type H (Table 4), [51,[64][65][66][67][68][69][70][71] structurally analogous to silanes of type C. In all cases, germanes H were prepared by reacting Li[(o-C 6 H 4 )PR' 2 ] with the appropriate dichloridogermane. Interestingly, the oxidative addition of the GeÀ H bond of hydridogermanes to low-valent metal complexes [64,65] could not be satisfactorily achieved in most cases.…”

“…Interestingly, the oxidative addition of the GeÀ H bond of hydridogermanes to low-valent metal complexes [64,65] could not be satisfactorily achieved in most cases. Most complexes derived from germanes of type H were prepared by oxidatively adding GeÀ X (X=F, [69,70] Cl, [51,[66][67][68][69] Me, [71] Ph [70] ) bonds to easily available low-valent metal complexes. Some of the resulting PGeP germyl have been used as catalyst precursors for reductive aldol-type reactions [65] and allene hydrocarboxylations.…”

“…[75] These complexes easily release a chloride anion from the tin atom, leading to cationic PSnP stannylene complexes. [64,65] H Ph Ph Pd [65] Cl Cl Ph Ir [51] , Pt [66] Cl Me Ph Pd [67] Cl Me 4-MeOC 6 H 4 Pd [67] Cl Ph Ph Pd [69] Pt [68] F Ph Ph Pd [69] F F Ph Ir [70] F Ph Ph Ir [70] Me Me Ph Rh [71] , Ir [71] Ph Ph Ph Ir [70] Table 5. PSnP stannanes of type I that have been used as precursors to PSnP stannyl complexes.…”