A series of h 3 -indenyl molybdenum compounds [(h 3 -4,7-Me 2 C 9 H 5 )Mo(CO) 2 ( N,N L)Cl] ( N,N L ¼ bpy, phen, pyma), isostructural with well-known h 3 -allyl compounds, was synthesized from the recently established halide synthon [{(h 5 -4,7-Me 2 C 9 H 5 )Mo(CO) 2 (m-Cl)} 2 ]. The low stability of the hexacoordinated h 3 -indenyl molybdenum species in solution has been overcome by a modification of the chelating ligand. Hence, the dissociation of the compounds bearing ligands with methyl groups beside nitrogen donor atoms (e.g. 6,6 0 -Me 2 -bpy, 2,9-Me 2 -phen; 2,9-Me 2 -4,7-Ph 2 -phen) is strongly disfavored due to the steric requirements of the substituents. The considerable discrimination of the pentacoordinated species enables the use of [(h 5 -4,7-Me 2 C 9 H 5 )Mo(CO) 2 (2,9-Me 2 -phen)][BF 4 ] for the assembly of derivatives bearing other halides and pseudohalides in the coordination sphere of molybdenum. The current study further describes some other new indenyl complexes accessible from [{(h 5 -4,7-Me 2 C 9 H 5 )Mo(CO) 2 (m-Cl)} 2 ]. All structural types presented in this experimental study were supported by X-ray crystallographic data.Scheme 1 Molecular formula of 1.Scheme 3 Reaction of 2 with two equivalents of bpy, phen and pyma.This journal is Fig. 3 ORTEP drawing of [(h 3 -C 3 H 5 )Mo(CO) 2 (pyma)Cl] (6-allyl). The labeling for all non-hydrogen atoms is shown. Thermal ellipsoids are drawn at the 30% probability level. Scheme 4 Synthesis of cationic molybdenum compounds.
This journal isScheme 9 Reaction of 2 with two equivalents of 3,4,7,8-Me 4 -phen and 4,4 0 -Me 2 -bpy.Scheme 10 Syntheses of complexes bearing 2,9-Me 2 -4,7-Ph 2 -phen and 6,6 0 -Me 2 -bpy.This journal is
