In sharp contrast to tetraphenyldiphosphine, which does not add to carbon-carbon double bonds efficiently, its monoxide, [Ph2 P(O)PPh2 ] can engage in a radical addition to various alkenes, thus affording the corresponding 1-phosphinyl-2-phosphinoalkanes regioselectively, and they can be converted into their sulfides by treatment with elemental sulfur. The phosphinylphosphination proceeds by the homolytic cleavage of the P(V) (O)-P(III) single bond of Ph2 P(O)PPh2 , followed by selective attack of the phosphinyl radical at the terminal position of the alkenes, and selective trapping of the resulting carbon radical by the phosphino group. Furthermore, the phosphinylphosphination product could be converted directly into its platinum complex with a hemilabile P,O chelation.

Bis‐phosphanated compounds are regarded as the most ubiquitous privileged ligand structures in transition‐metal catalysis. The development of highly atom economical reactions is of great importance for their syntheses because less atom economical methods often require complicated purification procedures under inert atmospheres to remove excess starting materials and byproducts. Herein, the photoinduced addition reactions of diphosphane monosulfides bearing PV(S)−PIII single bonds to alkenes is disclosed. These reactions require only equimolar amounts of the diphosphane monosulfide relative to the alkene and facilitate highly selective introduction of two different types of phosphorus‐containing groups, such as thiophosphoryl and phosphanyl groups, into a variety of alkenes without any catalyst, base, or additive.

The facile synthesis of organophosphorusc ompoundsi so fg reat importancef or the development of new synthetic methods by using air-stable sourceso fp hosphorus. In this respect, as ynthetic method that is based on ar eductiver earrangementa nd is capable of converting airstable pentavalent phosphorusc ompounds into reactive trivalent phosphorus compoundsi sapowerful tool. Tetraphe-nyldiphosphine disulfide, which is as helf-stable solid, was the focus of this study,a nd it was shown to undergo reductive rearrangement to trigger the bisthiophosphinylation of av ariety of alkenes,s uch as terminal, cyclic, internal, and brancheda lkenes,1 ,3-dienes,a nd terminal alkynes when exposed to light withoutany catalyst, base, or additive.Scheme1.Reductive rearrangement of TMDPO anddiphosphine disulfide.[a] Y.

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