Transition‐Metal‐Substituted Gallanes: Synthesis and Spectroscopic Studies of Highly Polar σ(M—Ga) Bonds, Structures of trans‐(Ph₃P)(CO)₃Co—Ga[(CH₂)₃N(C ₂H₅)₂]R (R = Cl, CH₃) and (n⁵‐C₅H₅)(CO)₂Fe—GaCl₂ [N(CH₃)₃]

Abstract

Abstract The salt elimination reaction of the transition carbonyl metal‐lates [L(CO) n M](Na/K) (M = Cr, Mo, W, Mn, Re, Fe, Co, Ni; L= CO, n 5 ‐C 5 R 5 , PR 3 ; n = 1‐4; R= alkyl, aryl) with the base‐stabilized galliumhalides Cl a GaR 3 ‐a(Do) (R = H, alkyl, halide; Do = THF, N(CH 3 ) 3 , NC 7 H 13 ) or Cl a Ga[(CH 2 ) 3 N‐R 2 ](R) 2 ‐ a yielded almost quantitatively the transition metal‐substituted, gallanes [L(CO) n M] a GaR 3 ‐ a (Do) and [L(CO) n ‐M] a Ga[(CH 2 ) 3 NR 2 ](R) 2 ‐ a , respectively. Residual halide functionalities in these complexes were selectively replaced by various other groups. The new compounds were characterized by means of elemental analysis, 1 H‐, 13 C‐, 31 P‐NMR, MS, and lR v(CO) data. The single‐crystal X‐ray structure analysis of trans ‐(Ph 3 P)(CO) 3 Co‐Ga[(CH 2 ) 3 N(C 2 H 5 ) 2 ](R)( 6s : R = Cl, 6t : R= CH 3 ) showed s̀(Co‐Ga) lengths of 237.78(4) and 249.5(1) pm, respectively. A short s̀(Fe‐Ga) contact of 236.18(3) pm was found for (n 5 ‐C 5 H 5 )(CO) 2 Fe‐Ga‐Cl 2 [N(CH 3 ) 3 ] ( 5a ). Low‐pressure MOCVD experiments were performed to give thin films of analytically pure CoGa alloy.