Phosphorus phosphandiides

It is a challenge to study dimetalated derivatives of primary phos-phanes that possess more covalent metal-phosphorus bonds. This can be achieved through replacement of the alkali metal ions in bimetallic phosphandiides by monovalent coin metal centers. 

In contrast to magnesium phosphandiides, analogous tin(II) derivatives possess more covalent metal-phosphorus bonds. This basic difference is also apparent for dilithium versus dicopper(I) phosphandiides (see Section II and III). It is, therefore, interesting to assess the structural and electronic features of such species in a similar way. To date, only three tin(II) phosphandiide derivatives have been prepared... 

The Sn6P6 cages 19c and 19d are accessible by two different Bronsted acid-base reaction pathways Reaction of lc and Id, respectively, with two different stannanediyl derivatives furnished in 80-89% yield red-black crystals of the aggregates (Eq. 12) (39). The tin(II) phosphandiides are somewhat related to the previously described oligomeric bis (phosphaneyl) stannanediyls of the type PkSn, which easily form intermolecular aggregates (50, 51) or remain monomeric, if the phosphorus atoms bear very crowded organosilyl substituents (52). 

An important result of the multinuclear NMR investigations of 23— 25, 27, 28, and 31-35 is that the structures, in contrast to aggregates of monometalated secondary phosphanes and arsanes, are retained in solution. Thus, the phosphandiide derivatives here discussed show resonance signals in their 31P NMR spectra that are independent of concentration and temperature (see Table III). The 31P and 27A1 NMR chemical shifts of 23-25, 27, and 31-35 differ with respect to ring size of the clusters and electronic influences by the substituents at phosphorus and aluminum. 

---