Gallium complexes phosphines

Indium and gallium coordination compounds containing phosphine ligands have recently aroused interest for their widespread application as intermediates in the preparation of the Group 13 - Group 14 semiconductors [4], Since the early reports about compounds with transition metal-indium bonds [51, relatively little research has been reported in this field. However there is a growing interest in the coordination chemistry and structural features of heterometallic indium [6] and gallium complexes [7] which are also attractive as potential precursors of new materials with particular properties. 

R3T1 compounds react readily with acids, halocarbons, or sulfur dioxide to form I TIX. They also form neutral complexes (R3TI L) with Lewis bases (L), eg, amines and phosphines, in a similar manner as the gallium and indium analogues. 

Gallium and Indium. Virtually nothing was known about the coordination chemistry of indium with tertiary phosphines until the pioneering work of Carty and Tuck. We allowed I2PR3 (R = Ph, Pr or Pr ) to react with indium metal powder, and obtained a series of interesting and novel complexes, Equations... 

Phosphine oxide complexes with aluminium or gallium trimethyl can be made by direct addition to the etherate (9.159), while dimeric phosphinate complexes can be made by slowly adding a benzene solution of a phosphinic acid to a trialkyl aluminium (9.160, 9.161) [11,12]. Large cages are obtained in Equations 9.162 and 9.163 [13,14]. Compounds (9.164) have Ga-O-P linkages. 

The synthesis, structure and bonding of the first aluminium(I) and gallium(I) complexes of phosphine-substituted transition metal centres have been published. These have terminal coordinated Cp E ligands (E = Al, Ga or In). Reaction of [(dcpe)Pt(H)(CH2Bu )] [dcpe = bis(dicyclohexylphosphino)ethane] with Cp E yields the tetrahedrally coordinated complexes [(dcpe)Pt(AlCp )2] (38) and [(dcpe)Pt(GaCp )2]. Quantum chemical calculations suggest rather weak Pt-E bonds for both complexes. 

---