Influence of highly basic phosphine ligand on the reactivity and hydrolysis of P 4 and P 4 S 3 supported by ruthenium fragments

Coordination Chemistry of P4S3 and P4Se3 towards the Iron Fragments [Fe(Cp)(CO)2]+ and [Fe(Cp)(PPh3)(CO)]+

“…[6,7] These complexes can enable interesting degradationchemistry of the otherwise inert cages under standard conditions. succeeded in the synthesis of complexes of yellow arsenic ([PPh 3 Au(As 4 )] + and [Cp*Ru(dppe)(As 4 )] + )t hrough the reactiono ft he corresponding transition-metal halide with Ag(As 4 ) 2 [Al(OR F ) 4 ]. [5] An ovel approach towards complexeso fw eak ligands, like the group 15/16 cages, are ligand-transfer reactions.…”

“…In such complexes,t he basal phosphorus atoms of thec age coordinate to them etal atom, or as in dimeric [{Ru(Cp)(PPh 3 ) 2 } 2 P 4 S 3 ] 2 + ,t he nortricyclane cage interacts with the metal fragments through the apical as well as one of the basal phosphorus atoms. [2,[3][4][5] Complexes of these transition-metal fragments with other inorganic cages as ligands, such as P 4 ,A s 4 ,a nd AsP 3 ,a lso exist;f or example, [Cp*Fe(dppe)(P 3 As)] + ,[ Cp*Fe(dppe)(P 4 )] + ,a nd [Cp*Ru-(dppe)(As 4 )] + . [6,7] These complexes can enable interesting degradationchemistry of the otherwise inert cages under standard conditions.…”

“…Thus, Scheeretal. succeeded in the synthesis of complexes of yellow arsenic ([PPh 3 Au(As 4 )] + and [Cp*Ru(dppe)(As 4 )] + )t hrough the reactiono ft he corresponding transition-metal halide with Ag(As 4 ) 2 [Al(OR F ) 4 ]. This acts as as table storage form of yellow arsenic that releases the As 4 cluster upon removal of the Ag + cation with aw ell-soluble halide complex.…”

“…However,t hey readily yield complexesw ith strongly coordinating ligands, such as phosphines. [9] Only recently, [ FpÀP 4 ] + and monophosphinesubstituted [FpPPh 3 ÀP 4 ] + that include dynamically bound P 4 cages, which are visible on the NMR timescale, were synthesized. [10] The formation of these complexes showed that it is possible to use the ligand-transfer reaction to bind weakl igands to these metal fragments through halide abstractions given that the ligand is immediatelypresent in the reactionenvironmentb yc oordination to the silver ion.…”

“…[11,[12][13][14] Hence, the concept of ligand-transfer chemistry can be tested by reactinge asily accessible representatives of thesec ompounds with suitable, soluble transition-metal halides. Herein, we present complexes of P 4…”