Multiply Bonded Metal(II) Acetate (Rhodium, Ruthenium, and Molybdenum) Complexes with the <i>trans</i>-1,2-Bis(<i>N</i>-methylimidazol-2-yl)ethylene Ligand

Fritsch, Nico; Wick, Christian R.; Waidmann, Thomas; Dral, Pavlo O.; Tucher, Johannes; Heinemann, Frank W.; Shubina, Tatyana E.; Clark, Timothy; Burzlaff, Nicolai

doi:10.1021/ic501435a

Cited by 22 publications

(29 citation statements)

References 99 publications

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“…The compounds investigated here are the previously reported 45 Ru 2 (chp) 4 (THF) (2) as well as the new axial adducts Ru 2 (chp) 4 (DMSO) (3; DMSO = dimethyl sulfoxide), Ru 2 (chp) 4 (PPh 3 ) (4), Ru 2 (chp) 4 (py) (5), and Ru 2 (chp) 4 -(MeCN) (6) and the new dimeric compounds [Ru 2 (chp) 4 ] 2 (7) and [Ru 2 (chp) 4 ] 2 (ZnCl 2 ) (8). Aside from 7, all of these compounds were characterized by X-ray crystallography and electronic absorption spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

Brown

Dolinar

Hillard³

et al. 2015

Inorg. Chem.

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Reduction of (4,0)-Ru2(chp)4Cl (1) (chp = 6-chloro-2-oxypyridinate) with Zn or FeCl2 yields a series of axial ligand adducts of the Ru2(II,II) species Ru2(chp)4(L), with L = tetrahydrofuran (2), dimethyl sulfoxide (DMSO; 3), PPh3 (4), pyridine (5), or MeCN (6). Zn reduction in noncoordinating solvents such as toluene or CH2Cl2 leads to the dimeric species [Ru2(chp)4]2 (7) or [Ru2(chp)4]2(ZnCl2) (8), whereas addition of strongly σ-donating ligands such as CO causes cleavage of the Ru-Ru bond. Density functional theory (DFT) models of these complexes, the axially free species, and the axial adducts of several other potential ligands (H2O, NH3, CH2Cl2, S-bound DMSO, N2, and CO) indicate that these compounds can be divided into three distinct categories, based on their Ru-Ru bond length and electronic structure. Compounds 2, 3, 5, 6, 7, and 8, the hypothetical axially free species, and adducts of H2O and NH3 fit in Category 1 with a (δ*)(2)(π*)(2) ground state, as indicated by their electronic spectra, magnetic properties, and Ru-Ru bond distances. However, compound 4 and the CH2Cl2 adduct (Category 2) show a pseudo-Jahn-Teller distortion and spectroscopic signs of δ*/π* orbital mixing suggestive of a new electronic ground state intermediate between the (δ*)(2)(π*)(2) and (δ*)(1)(π*)(3) configurations. Category 3 consists of the hypothetical adducts of N2, S-bound DMSO, and CO, all of which are predicted to have a (δ*)(1)(π*)(3) configuration. Electronic spectra were recorded and assigned using time-dependent DFT, allowing assignment of a band in the 10,000-13,000 cm(-1) range as the δ → π* transition. The axial ligand's π-acid character heavily influences the δ*-π* gap, and thereby the ground-state electronic configuration, but not the axial ligand binding strength, which is dictated more by the σ-donor character of the ligands. Thus, this work greatly expands the number of axial ligand adducts known for Ru2(II,II) complexes supported by N,O-donor ligands and provides a predictive theoretical framework for their stability and electronic structures.

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Section: Introductionmentioning

confidence: 99%

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

Brown

Dolinar

Hillard³

et al. 2015

Inorg. Chem.

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“…[17] CASSCF/CASPT2 and DFT calculations of a single periodic unit of [Ru 2 (Ac) 4 (trans-bie) 2 ] n indicated a Ru=Ru bond with an effective bond order (EBO) of 1.7. [7] This inspired us to study 1D coordination polymers [Ru 2 (OAc) 2 (CO) 4 A small library of N,N-bridging ligands L was applied in this study, consisting of trans-bie (L1), pyrazine (pyz) (L2), 4,4′-bipyridine (4,4′-bipy) (L3), 1,2-di(4-pyridyl)ethylene (bpe) (L4) and 1,4-diazabicyclo[2.2.2]octane (DABCO) (L5), which are shown in Figure 3. All five ligands L1-L5 are ideal for forming linear or quasilinear 1D chains by bridging metal centres but vary regarding their σ and π interactions as well as their π conjugation.…”

Section: Resultsmentioning

confidence: 99%

“…[7] The results are summarized in Table 3 and Figure 6. The metal-metal Mayer bond orders (MBO) [23] of 0.69 and 0.66 for model complexes 1 and 2, respectively, and the effective bond order (EBO) [24] of 0.89 indicate a weakening of a possible single bond (σ orbitals) due to ligand coordination.…”

Section: Resultsmentioning

confidence: 99%

“…2 (μ-OAc) 4 }(μ-trans-bie)] n , [6,7] in which paddlewheel building blocks of various metal(II) acetates (M = Cu, Cr, Mo, Rh, Ru) are chained together by the trans-bie ligand (Scheme 1). Scheme 1.…”

Section: Nn-donor Ligand Trans-12-bis(n-methylimidazol-2-yl)ethylenmentioning

confidence: 99%

“…Synthesis of paddlewheel 1D coordination polymers with transbie. [7] For a 1D coordination polymer based on the copper(II) acetate paddlewheel unit, the absorption behaviour and electronic properties were investigated by scanning tunnelling microscopy (STM) measurements on highly ordered pyrolytic graphite (HOPG). This polymer showed interesting properties towards metal-ligand-derived semiconducting nanowires.…”

Section: Nn-donor Ligand Trans-12-bis(n-methylimidazol-2-yl)ethylenmentioning

confidence: 99%

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The aim of the present work was to test various chiroptical techniques, including in particular the in situ dirhodium methodology, to assign the absolute configuration of 1,2- and 1,3-amino alcohols. As models, we selected mainly compounds that have both an additional strongly absorbing and interfering chromophoric system and application in medicinal chemistry. Determination of the absolute configuration (AC) of the tested molecules such as cinchona alkaloids, Tamiflu, and others was carried out using a combination of electronic and vibrational circular dichroism (ECD, VCD) spectroscopy. It has been demonstrated that both 1,2- and 1,3-aminol moieties are subject to the same sector rule correlating stereostructure of formed Rh -complex with chiroptical properties, and that the changes in the position of the stereogenic center do not affect its proper use.

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Multiply Bonded Metal(II) Acetate (Rhodium, Ruthenium, and Molybdenum) Complexes with the trans-1,2-Bis(N-methylimidazol-2-yl)ethylene Ligand

Cited by 22 publications

References 99 publications

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

1D Chains of Diruthenium Tetracarbonyl Sawhorse Complexes

Chirality sensing of bioactive compounds with amino alcohol unit via circular dichroism

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Multiply Bonded Metal(II) Acetate (Rhodium, Ruthenium, and Molybdenum) Complexes with the trans-1,2-Bis(N-methylimidazol-2-yl)ethylene Ligand

Cited by 22 publications

References 99 publications

Electronic Structure of Ru2(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

Electronic Structure of Ru2(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

1D Chains of Diruthenium Tetracarbonyl Sawhorse Complexes

Chirality sensing of bioactive compounds with amino alcohol unit via circular dichroism

Contact Info

Product

Resources

About

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding