Preparation and reactivity of diazoalkane complexes of ruthenium stabilised by an indenyl ligand

Diazoalkane complexes of ruthenium with tris(pyrazolyl)borate and bis(pyrazolyl)acetate ligands

“…In particular, the IR spectra show a medium-intensity band at 1959-1900 cm −1 , attributed to the ν CvNvN of the coordinated diazoalkane. Comparison of this value with those of the related complexes whose X-ray structures are known [1][2][3][4][7][8][9][10] suggests an end-on η 1 -coordination mode for the Ar1Ar2CN 2 ligand. In the spectra, a strong band at 1672-1669 cm −1 is also present, and was attributed to the Some reactivity studies on diazoalkane complexes 4 were performed with alkenes and alkynes, to test whether substitution or (3 + 2) cycloaddition occurred.…”

“…4g Dipolar (3 + 2) cycloaddition of coordinated diazoalkane with alkene and alkyne, affording 3H-pyrazole derivatives, 8 as well as hydrolysis, yielding η 2 -diazene derivatives has recently been reported. 9 In recent years, we have been interested in the chemistry of diazoalkane complexes [7][8][9][10]13 and have reported the synthesis and reactivity of these types of compounds having p-cymene, η 5 -C 5 H 5 , η 5 -C 5 Me 5 and indenyl as supporting ligands. As the reactivity of the coordinated N 2 CAr1Ar2 group in these complexes is strongly influenced by the nature of ancillary ligands, we thought of extending our study to the comparable tris( pyrazolyl)borate (Tp) ligand, 14 to test whether stable diazoalkane complexes could be prepared and to understand how their properties changed.…”

“…[1][2][3][4][7][8][9][10] In addition, diazoalkane complexes may be of interest as models for understanding N 2 coordination and functionalisation. 11,12 A number of diazoalkane complexes of several metals have been reported [1][2][3][4][7][8][9][10] and their reactivity studies have highlighted various pathways, depending on the coordination mode and the nature of ancillary ligands. Thus, extrusion of dinitrogen with carbene formation was observed in η 2 -CN-coordinated species, 4f,5,6 whereas an η 1 -N-bound diazoalkane can yield dinitrogen [M]-N 2 complexes, 4f convert carbene to imine, 5f or cleave the N-N bond of the N 2 CAr1Ar2 group.…”

Reactions of Iron(II) Complexes Supported by Tripodal Amido-Phosphine-Amido Ligands with Diazo Compounds

“…Complex 3 has been characterized by 1 H NMR, 13 C NMR, and 31 P NMR spectroscopies, 57 Fe Mössbauer spectroscopy, infrared spectroscopy, single-crystal X-ray diffraction, as well as elemental analysis. The molecular structure of 3 established by X-ray diffraction study revealed a side-on coordination mode of the diazoalkane ligand that has the Fe-N2 and Fe-N1 distances of 0.17524(11) and 0.19601(11) nm, respectively (Figure 2).…”

“…[6][7][8][9][10] Consequently, there are great interests on the sythesis, structural feature, and reactivity of transition-metal diazoalkane complexes. The known transition-metal diazoalkane complexes are dominated by the complexes of cobalt, nickel, and ruthenium, [11][12][13][14][15][16] whereas the diazoalkane complexes of iron are scarce, which form a sharp contrast to the soaring research interest on iron-catalyzed carbenetransfter reactions. [17] The limited examples of iron diazoalkane complexes include the bis(imino)pyridine complex [(PDI)Fe(η 1 -N 2 CH-SiMe 3 )] (A in Chart 1), [18] the tris(pyrrolido)ethane iron complex [(tpe)Fe(η 1 -N 2 CPh 2 )][Li(THF) 4 ] (tpe＝tris(5-mesitylpyrrolyl)ethane, B), [19] the β-diketiminate iron complex [L Bu-t Fe(η 1 -N 2 CPh 2 )] (L Bu-t ＝ [(DippNCBu t ) 2 CH] -, C) [20] , the cyclopentadienyliron complexes [(η 5 -C 5 H 5 ) Fe(η 1 -N 2 C-Ar 1 Ar 2 )(P-P)]BPh 4 (P-P＝1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane; Ar 1 ＝ Ar 2 ＝ Ph; Ar 1 ＝Ph, Ar 2 ＝p-tolyl; Ar 1 Ar 2 ＝C 12 H 8 , D), [21] as well as the side-on type diazo complexes [(PDI)Fe(η 2 -N,N-N 2 C-Ph 2 )] (E) [22] and [L Bu-t Fe(η 2 -N,N-N 2 CPh 2 )K(OEt 2 )] 2 (F) [20] .…”