Crystal Structure of Polymeric Li(thf)PHCy (thf = Tetrahydrofuran, Cy = Cyclohexyl): A Pseudo One-Dimensional Twisted Ladder

Synthetic and structural developments in hetero-s-block-metal chemistry: new ring-laddering, ring-stacking and other architectures

“…Another twisted ladder polymer, but one having full rather than selective solvation, is known for the lithium primary phosphide {[Cy-P(H)Li•THF] ∞ }. 13 However, as yet, there is still no example of a crystallographically characterised pure, donor-free, lithium amide (or phosphide) polymeric ladder.…”

Structural direction by the dominant metal

“…Although we agree that thermodynamic considerations generally play the greatest role in dictating the outcomes of the variety of reactions discussed above and the structures of the heterometallic complexes formed, our conclusion is that structural direction by the primary amido lithium complexes is unlikely and that the bonding demands of the p block metals dominate the kinetics and thermodynamics involved. In this regard, it is noteworthy that the infinite ladder structure of the primary phosphido lithium complex [(CyPH)Liؒthf] ∞ 21 (which has previously been structurally characterised) 15 has no bearing on the structure of [{Sb(PCy) 3 } 2 Li 6 ]ؒ6Me 2 NH 8 formed in its reaction with Sb(NMe 2 ) 3 3e and that the reaction of the cyclic ladder [(Bu t NH)Li] 8 itself with Sb(NMe 2 ) 3 gives [{Sb(NBu t ) 3 } 2 Li 6 ] 22, containing the expected Sb 2 N 6 Li 6 core (Fig. 13).…”

Terminal Alkylphosphanylidene Organo­tantalum(V) Complexes

“…Reduction could be avoided by employing the bisamido complex [Cp*Ta{1,2‐(NSiMe 3 ) 2 C 6 H 4 }Cl 2 ]9 ( 1 ) as the starting material. Thus, complexes [Cp*Ta{1,2‐(NSiMe 3 ) 2 C 6 H 4 }(PR)] [R = Cy ( 2 ), i Pr ( 3 )] are readily available from 1 and two equivalents of lithium phosphanide (LiPHCy, LiPH i Pr)8a in toluene at –80 °C (Scheme ).…”