The transition metal-gallium complexes [Ga(MLJ3] [where ML, = Fe(C0)2(q-C5H5), M o ( C O )~(~-C~H~) , Co(C0)3(PPh3), and Mn(CO),] have been synthesised by salt elimination between GaC13 and M'(ML,) (MI = Na/K). The iron complex [Ga{Fe(C0)2(q-C5H5)]31 (1) has been characterised by X-ray crystallography and shown to contain a planar, three-coordinate gallium centre bound to three Fe(C0)2(q-C5H5) fragments by unsupported Ga-Fe bonds [av. 2.444(1) A]. A partial struc-(5) is consistent with a trigonal-planar GaMo3 core. Brief mention is also made of two chloro complexes (GaCl(ML,),] [ML, = Fe(CO)2(q-C5-H5) and Co(CO), (PPh,)].Compounds containing both gallium and a transition metal are currently of interest as potential single-source precursors to binary intermetallic phases. Such interest stems from the fact that certain phases are useful as Schottky barriers and Ohmic contacts to 13 -15 semiconductors and, in this regard, we note a recent paper by Chen et al."] concerning the chemical vapour deposition of CoGa and PtGa, from precursor molecules containing these respective elements. Nevertheless, such applications are likely to be limited at present by the relative paucity of known compounds containing gallium and a transition metal.The most extensive studies on transition metal-gallium complexes have been carried out by Haupt and coworkers over a number of years. The compounds which have been [R~Z(C~)~(PP~~)Z(C~-~)Z{~-G~R~(CO)~(PP~~)}I['~, Na[CL,-Ga{Mn(CO)s},] (n = 1-3) [61, and [Re3(C0) Herein we report details on some of our own studies on transition metal-gallium complexes. Results and DiscussionThe reaction between GaC13 and three equivalents of Na[Fe(C0)2(q-C5HS)] afforded, after workup and recrystallisation from THF/hexane mixtures, dark red crystals of the triiron-gallium complex 1, and it was evident from a solution infrared spectrum [ Table 1, Figure l(a)] that this complex was very similar to the indium analogue 2[l8]. The molecular structure of 1, as determined by X-ray crystallography, is
The reaction between InCl3 and 3 equiv of Na[Mo(CO)3(7j-C5H5)] affords the trimolybdenum-indium complex [In¡Mo(CO)3-( -05 5•))3] (2), the structure of which was established by X-ray crystallography. Compound 2 crystallizes in the monoclinic space group P2\/n with a = 11.463 (1) A,b = 17.854 (1) A, c = 13.572 (1) ,ß= 101.846 (8)°, and Z = 4. The structure comprises a central trigonal-planar indium atom bonded to three Mo(CO)3(t7-C5H5) fragments via In-Mo bonds. The corresponding reaction between InCl3 and 2 equiv of Na[Mo(CO)3(i7-C5H5)] affords the anionic dimolvbdenum complex [InCl2(Mo(CO)3(tj-C5H5)(2]•, which was also characterized by X-ray crystallography. It crystallizes as the sodium salt, THF solvate [Na(THF)2] [InCl2|Mo-(CO)3(t/-C5H5))2] (6) in the triclinic space group P\ with a = 10.750 (2) A, b = 12.457 (2) Á, c = 13.609 (2) A, a = 108.569 (7) °, ß = 95.829 (7)°, and y = 112.248 (6)°a nd contains dimeric units linked by Cl-Na-Cl bridges, each sodium atom being ligated by three chlorines, two THF molecules, and the oxygen of one of the molybdenum-bound carbonyls; Z = 1 dimer per unit cell. Reaction between InCl3 and 1 equiv of [ ( )3( -5 5)] also affords an anionic complex, [InCl3{Mo(CO)3(t;-C5H5)|]", characterized by X-ray crystallography. It crystallizes as the sodium salt, THF solvate [Na(THF)2] [InCl3|Mo(CO)3(7)-C5H5)|] (8) in the monoclinic space group P2{/c with a = 10.160 (1) Á, b = 21.116 (2) Á, c = 11.862 (1) A, and ß = 109.304 (7)°a nd also comprises dimeric units linked by Cl-Na-Cl bridges; Z = 2 dimers per cell. The tungsten analogues of the above three complexes were also prepared and characterized by spectroscopic means. Details of the solution-state properties of all compounds as determined by infrared spectroscopy are discussed.
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