Gallaphosphene L(Cl)GaPGaL: A novel phosphinidene transfer reagent
Mahendra K. Sharma, Hanns M. Weinert, Christoph Wölper, Stephan Schulz
Abstract
Abstract Gallaphosphene L(Cl)GaPGaL 1 (L=HC[C(Me)N(Ar)] 2 ; Ar=2,6‐ i Pr 2 C 6 H 3 ) reacts with N ‐heterocyclic carbenes R NHC ( R NHC=[CMeN(R)] 2 C; R=Me, i Pr) to R NHC‐coordinated phosphinidenes R NHC→PGa(Cl)L (R=Me 2 a , i Pr 2 b ) and with isonitriles RNC (R= i Pr, Cy) to 1,3‐phosphaazaallenes L(Cl)GaP=C=N−R (R= i Pr 3 a , Cy 3 b ), respectively. Quantum chemical calculations reveal that 2 a / 2 b possess two localized lone pair of electrons, whereas 3 a / 3 b only show one localized lone pair as was reported for gallaphosphene 1 . 2 b reacts with 2.5 equivalents of a borane (THF ⋅ BH 3 ) to the NHC‐stabilized phosphinidene‐borane complex [ i Pr NHC→P(BH 2 )] 2 (BH 3 ) 3 4 with concomitant formation of LGa(H)Cl 5 . 2 – 5 are characterized by heteronuclear ( 1 H, 13 C{ 1 H}, 31 P{ 1 H}) NMR and IR spectroscopy, elemental analysis, and single crystal X‐ray diffraction (sc‐XRD).