A Sterically Encumbered 13/15 Cycle and its Cleavage with N-heterocyclic Carbenes and other Lewis Bases

作者：Kapitein Manuel; Balmer Markus; von Haenisch Carsten^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2016, 642(22): 1275-1281.

DOI：10.1002/zaac.201600263

• NHC-stabilization
• Group 13 complex
• Galliumphosphanide
• Lewis acid
• base adducts
• Main group complexes

Herein, the latest results on the topic of NHC-stabilized, monomeric group 13 metalsilylphosphanides, with the focus on the sterically demanding [GatBu(2)R(x)]-fragment (x = 1, 2) are presented. The synthesis and characteristics of the cyclic compound [tBu(2)GaP(H)SitBuPh(2)](2) (1), followed by the cleavage of this cycle with different Lewis bases like pyridine, DMAP or the IiPr carbene is described for the first time. The compounds [(LB)tBu(2)GaP(H)SitBuPh(2)] [LB = pyridine (2) and LB = DMAP (3)] are investigated as possible precursors for ligand exchange reactions with sterically demanding NHCs like IMes or IDipp, since the latter show no reaction with the four-membered cycle 1 due to their high steric strain. The pros and cons of an alternative pathway for the synthesis of monomeric complexes by means of salt elimination are pointed out.

• 出版日期2016-11