Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with α-diimine ligands. X-ray structure of [(CO)5MnRu(Me)(CO)2(σ(N′)-iPr-PyCa)] (iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine)

Abstract

Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with alpha-diimine ligands. X-ray structure of [(CO)5Mn-Ru(Me)(CO)2(sigma(N')-iPr-PyCa)](iPr-PyCa = pyridine-2-carbaldehyde-Nisopropylimine) Nieuwenhuis Oskam, A., & Goubitz, K. (1995). Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with alpha-diimine ligands. X-ray structure of [(CO)5Mn-Ru(Me)(CO)2(sigma(N')-iPr-PyCa)](iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine). Inorganica Chimica Acta, 232, 19-25. DOI: 10.1016/0020-1693(94)04360-8 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with t -diimine ligands. X-ray structure of [(CO)sMn-Ru(Me) (CO)a(a(N),a(N') Received 4 July 1994; revised 6 September 1994 AbstractThe synthesis and spectroscopy of the complexes [(CO)sMn-Ru(Me)(CO)2(a-diimine)] (a-diimine=N,N'-diisopropyl-l,4-diaza-l,3-butadiene (iPr-DAB), pyridine-2-carbaldehyde-N-isopropylimine (iPr-PyCa)) are reported. The metal fragments are bonded to each other by an uncommon manganese-ruthenium bond. The single crystal X-ray structure has been determined. The purple crystals of [(CO)sMn-Ru(Me)(CO)2(iPr-PyCa)] are monoclinic, space group P21/n, Z=4, with unit cell dimensions a = 9.6297(7), b = 20.923(1), c = 10.166(1) ~ and fl = 92.190(8) °. The structure refinement converged to R = 0.035 for 3277 observed reflections. Both complexes show a strong, solvatochromic absorption band in the visible region, which is assigned to Ru (d,~)~a-diimine (~-*) transitions. In agreement with this assignment, the Raman spectra show resonance enhancement of Raman intensity for vs(CO) and vs(CN) of the Ru(Me)(CO)2(a-diimine) fragment.

Photochemistry of the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)]. Crystal structure of the photoproduct [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2]

“…iPr-PyCa iPr-DAB sorption band of these complexes was assigned to MLCT transitions [18]. In contrast, the emission of these [(CO)hMn-Ru(MeXCO)z(a-diimine)] complexes in a 2-MeTHF glass at 77 K had a much longer lifetime and lower quantum yield than might be expected for a lowest MLCT state [19].…”

“…The fractional coordinates, selected bond lengths and selected bond angles for the photoproduct are listed in Tables 3, 4 and 5, respectively. The complex contains an Mn and an Ru fragment connected by a o metal-metal bond of length 2.80 A, which is shorter than the corresponding bond in the parent complex (2.99 ,~) [18]. In addition, the ipr-PyCa ligand now forms a bridge between the two metal fragments, being tr(N1)-tr(N2)-bonded to Ru and r/E-(C1-N1) to Mn.…”

“…A similar excited-state process was found for population of the D ~ a-diimine excited state of the chromophore-quencher complexes [Re(D)(CO)3(a-diimine)] + (D = electron donor) [15-171. We have recently prepared two complexes [(CO) 5-Mn-Ru(Me)(CO)2(a-diimine)] [a-diimine = pyridine-2-carbaldehyde-N-isopropylimine (ipr-PyCa) or N,N'-diisopropyl-l,4-diaza-l,3-butadiene (ipr-DAB)] (see Fig. 1) and studied their spectroscopic properties [18] and emission spectra at low temperature [19]. By the use of resonance Raman spectroscopy, the visible ab-....... co\ ./ CO---Mn Ru …”

Spectroelectrochemical (UV−Vis, IR, NMR, and EPR) Study of the Inorganometallic Complexes Ru(E)(E‘)(CO)2(iPr-DAB) (E = Cl, E‘ = SnPh3, PbPh3; E = Me, SnPh3, GePh3, E‘ = SnPh3; E = E‘ = PbPh3; iPr-DAB = 1,4-Diisopropyl-1,4-diaza-1,3-butadiene)

“…The photochemical, photophysical, and redox properties of the complexes [M(E)(CO) 3 (α-diimine)] n (M = Mn, Re; n = 0, +1; E = halide, alkyl, PR 3 , donor solvent, etc.) were shown in numerous studies to be strongly determined by the nature and combination of the α-diimine and the axial ligand E. In this respect the related complexes [Ru(E)(E‘)(CO) 2 (α-diimine)] n are more versatile candidates for the widely ranged investigation of the energy- and electron-transfer reactions, luminescence properties, and radical reactivity, since both axial ligands E and E‘ can be varied independently …”

Synthesis of Heterobimetallic RuMn Complexes and the Coupling Reactions of Epoxides with Carbon Dioxide Catalyzed by these Complexes

“…[16] Note that for one of the carbonyl ligands attached to the manganese center, the Mn-C-O angle [Mn1-C10-O5, 167.3(4)8] deviates more from linearity than those of the other CO ligands on the manganese atom. Moreover, the distance of the carbon atom of this less linear carbonyl ligand on manganese from the ruthenium center measures 2.656(4) ; this relatively short distance is indicative of the presence of a weak interaction between this CO group and the ruthenium center.…”