Novel indenyl ligands bearing electron-withdrawing functional groups

Abstract

A series of molybdenum complexes bearing new ligands is reported. The study covers a series of molybdenum compounds with the Z 5 -coordinated indenyl ligand substituted with acyl-, ester-and amide-functions. This portfolio was extended by adding one representative with a Z 3 -coordinated estersubstituted indenyl ligand. The functionalized indenes, necessary for the assembly, were prepared by convenient routes starting from inexpensive and readily available materials, enabling their production on a multigram scale. All structural types presented in this experimental study were supported by X-ray crystallographic data.a Distances are given in Å; angles and dihedral angles are given in 1. b O is the envelope fold angle defined for the indenyl ligand as the angle between planes defined by C1, C2 and C3 and that of C1, C3, C8 and C9. 22 c D(M-C) represents the differences in the metal-carbon bonds. It is defined for the indenyl compounds as the difference between the averages of the metal-carbon distances M-C8 and M-C9 and those of M-C1, M-C2, and M-C3. 22 d Data for Ind. e Data for 1-(MeOCO)C 9 H 6 .Scheme 4 Synthesis of a mixed indenyl molybdenum complex. NJCPaper

Electron‐Deficient Imidazolium Substituted Cp Ligands and their Ru Complexes

“…In addition, we carriedo ut the NBO population analysiso f the hypothetical 1,2-disubstituted non-annellated compound 14 to compare the influence of the substitutionpattern. A1 ,2-substitution leads to ad ifferent dipole momento ft he molecule, but interestingly to the same charge of the Cp fragment.T herefore, we can assign the observed lower electron density of the Cp ring in the annellated system 9 to the fixed À counterions are omittedf or clarity.Selectedb ond lengths []and angles [8]: C13ÀC14 1.424(2), C18ÀC191 .414(2), C15ÀC201.457(2), C14ÀC15 1.414(2), C15ÀC16 1.411(2), C16ÀC17 1.390(2), C17ÀC18 1.400(2), C14ÀC18 1.453 (2) planar geometry of the imidazolium substituents and not to the substitution pattern.…”

“…Ar, [4] F, [5] Cl, [5] CN, COOR, NO 2 , CF 3 , [6] phosphonium, [7] pyridinium or ammonium groups)a re much less studied. [8,9] One interesting ligand class in this regard is that of cyclopentadienylides. These zwitterionic compounds are thermodynamically stable Cp compounds containing at least one a-cationic substituent at the Cp ring, e.g.…”

Facile Synthesis of 3-Arylindenes by HMPA-Promoted Direct Arylation of Indenes with Aryl Fluorides

“…9 The conventional method for the preparation of 3-substituted indenes involves first formation of indenyl lithium, generated in situ by deprotonation of indene with n -butyl lithium and subsequently reaction with electrophiles (Scheme 1b–d). 10 This method suffers from several drawbacks, such as the use of very low temperatures, long reaction time, and unsatisfactory regioselectivity. In addition, although the alkyl halides are good substrates for alkylation of indenyl anions, 11 rare examples have been reported for direct arylation of indenyl lithium with fluoroarenes or other haloarenes.…”

Stabilization of η3-indenyl compounds by sterically demanding N,N-chelating ligands in the molybdenum coordination sphere

“…The solid state structure of the compound 6a was determined by X-ray diffraction analysis, see 22,42,43 According to the initial aim, the compound 6a is isostructural with allyl complex [(h 3 -C 3 H 5 )Mo(CO) 2 (pyma)Cl] (6-allyl) that was also conrmed by X-ray diffraction analysis (cf. Fig.…”