The copper-catalyzed Click reaction of phenyl azide with ethynylphosphine oxides provides new P-substituted triazoles. With tris(ethynyl)phosphine oxide this route affords a versatile scorpionate ligand that coordinates to RhCl 3 as a tripodal N ligand. Upon reduction, the same ligand can act as a P donor to W(CO) 5 . Both coordination modes can be combined, giving access to a bimetallic Mo/W complex.

The phosphinidene complex iPr 2 N−PFe(CO) 4 was prepared as a storable phosphirane solution from Collman's reagent and iPr 2 NPCl 2 in the olefins 1-pentene and 1-hexene. The carbenelike reagent is able to hop under very mild conditions (>−25 °C) from one olefin to another and to alkynes to give the more stable phosphirenes that likewise display dynamic covalent behavior. The olefinic solutions are effective reservoirs for the highly reactive phosphinidene complex, as is illustrated in its N−H and O−H insertion reactions with amines, alcohols, and carboxylic acids and in its P−C bond formation with Grignard reagents.

Phosphorus-based macrocycles with acetylenic scaffolds have been built from acetylene-substituted phosphane oxides that were formed from diisopropylphosphoramidic dibromide (3) and an acetylenic Grignard reagent. The fourand six-edged macrocycles 15 and 16, in which the iPr 2 NP(O) units are connected through 1,3-butadiyne rods, were obtained from the monosilylated derivative of iPr 2 NP(O)(C 2 H) 2 (7) by multiple acetylene coupling reactions under oxidative

In this paper, we highlight the synthesis of av ariety of primary phosphine-boranes (RPH 2 •BH 3)f rom the corresponding dichlorophosphines,s imply by using Li[BH 4 ]a sr eductanta nd providero ft he BH 3 protectingg roup. The methodo ffers facile access not only to alkyl-and arylphosphine-boranes, but also to aminophosphine-boranes (R 2 NPH 2 •BH 3)t hat are convenient buildingb locks but without the protecting BH 3 moiety thermally labile and notoriously difficult to handle.T he borane-protected primary phosphines can be doubly deprotonated using n-butyllithium to provides oluble phosphanediides Li 2 [RP•BH 3 ]o fw hich the phenyl-derivative Li 2 [PhP•BH 3 ]w as structurally characterized in the solid state.