One pot synthesis of dimanganese carbonyl complexes containing sulfur and phosphorus donor ligands using tricarbonylpentadienylmanganese

Reyes‐Lezama, Marisol; Höpfl, Herbert; Zúñiga-Villarreal, Noé

doi:10.1016/j.jorganchem.2007.12.015

Cited by 11 publications

(11 citation statements)

References 16 publications

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“…This building block approach allowed the synthesis of the first dithiolato-bridged MnFe complexes. Related dimanganese dithiolate complexes had been reported by Treichel . The most curious property of [(CO) 3 Mn(pdt)Fe(CO) 2 (dppe)] + is its tendency to decarbonylate upon 1e-reduction.…”

Section: Discussionmentioning

confidence: 84%

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Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

et al. 2014

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Reported are complexes of the formula Fe(dithiolate)(CO)2(diphos) and their use to prepare homo- and heterobimetallic dithiolato derivatives. The starting iron dithiolates were prepared by a one-pot reaction of FeCl2 and CO with chelating diphosphines and dithiolates, where dithiolate = S2(CH2)22– (edt2–), S2(CH2)32– (pdt2–), S2(CH2)2(C(CH3)2)2– (Me2pdt2–) and diphos = cis-C2H2(PPh2)2 (dppv), C2H4(PPh2)2 (dppe), C6H4(PPh2)2 (dppbz), C2H4[P(C6H11)2]2 (dcpe). The incorporation of 57Fe into such building block complexes commenced with the conversion of 57Fe into 57Fe2I4(iPrOH)4, which then was treated with K2pdt, CO, and dppe to give 57Fe(pdt)(CO)2(dppe). NMR and IR analyses show that these complexes exist as mixtures of all-cis and trans-CO isomers, edt2– favoring the former and pdt2– the latter. Treatment of Fe(dithiolate)(CO)2(diphos) with the Fe(0) reagent (benzylideneacetone)Fe(CO)3 gave Fe2(dithiolate)(CO)4(diphos), thereby defining a route from simple ferrous salts to models for hydrogenase active sites. Extending the building block route to heterobimetallic complexes, treatment of Fe(pdt)(CO)2(dppe) with [(acenaphthene)Mn(CO)3]+ gave [(CO)3Mn(pdt)Fe(CO)2(dppe)]+ ([3d(CO)]+). Reduction of [3d(CO)]+ with BH4– gave the Cs-symmetric μ-hydride (CO)3Mn(pdt)(H)Fe(CO)(dppe) (H3d). Complex H3d is reversibly protonated by strong acids, the proposed site of protonation being sulfur. Treatment of Fe(dithiolate)(CO)2(diphos) with CpCoI2(CO) followed by reduction by Cp2Co affords CpCo(dithiolate)Fe(CO)(diphos) (4), which can also be prepared from Fe(dithiolate)(CO)2(diphos) and CpCo(CO)2. Like the electronically related (CO)3Fe(pdt)Fe(CO)(diphos), these complexes undergo protonation to afford the μ-hydrido complexes [CpCo(dithiolate)HFe(CO)(diphos)]+. Low-temperature NMR studies indicate that Co is the kinetic site of protonation.

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Section: Discussionmentioning

confidence: 84%

“…Related dimanganese dithiolate complexes had been reported by Treichel. 38 The most curious property of [(CO) 3 Mn(pdt)Fe(CO) 2 (dppe)] + is its tendency to decarbonylate upon 1e-reduction. The resulting complex, (CO) 3 Mn(pdt)Fe(CO)(dppe), is electronically related to the mixed-valence “H ox -models” [Fe 2 (pdt)(CO) 6– x L x ] + .…”

Section: Discussionmentioning

confidence: 99%

Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

et al. 2014

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“…We suggest that the reaction time (2.5 h) is dependent on the dppe nucleophilicity in view of the fact that when aryl and alkyl mercaptans are made to react with 1 in the presence of dppe, similar reaction times are observed. 8 Crystallization of complex 2 from a mixture of dichloromethane/hexane at low temperature afforded suitable crystals for an X-ray analysis. The ORTEP diagram is shown in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

“…The reaction chemistry of benzeneselenol toward 1 in the presence of triphenylphosphine turned out to be similar to that of mercaptans. 8 It is well known that arylselenols are better nucleophiles than arylthiols. 12 In the present case the reaction time for 3 (8 h) was longer than that reported for the sulfur analogue [Mn 2 (CO) 4 (μ-CO)(μ-SPh) 2 (PPh 3 ) 2 ] (40 min).…”

Section: Resultsmentioning

confidence: 99%

Tricarbonyl[(1−5-η)-pentadienyl]manganese: A Source of Benzeneselenolatomanganese Derivatives of Diverse Nuclearity

2010

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“…The Mn–Mn interaction in 15 is weaker than the Fe–Fe interaction in the similar Fe 2 (CO) 6 (μ-S 2 ) according to QTAIM analyses . Complex 18 and 19 contain the PPh 3 ligand, where 18 with a (μ-Se 2 ) ligand has an R MM value of 2.702 Å (Belletti) while the complexes in entry 19 with thiolate and selenolate ligands have Mn–Mn distances ranging from 2.64 to 2.69 Å (Reyes-Lezama , ).…”

Section: Manganese–manganese Bondsmentioning

confidence: 99%

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

2018

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This survey of metal–metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) n+, (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. The combination of experimental and computational results leads us to propose for the first time the ranges and “best” estimates for MM bond distances of all types (Ti–Ti through Zn–Zn, single through quintuple).

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One pot synthesis of dimanganese carbonyl complexes containing sulfur and phosphorus donor ligands using tricarbonylpentadienylmanganese

Cited by 11 publications

References 16 publications

Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates

Tricarbonyl[(1−5-η)-pentadienyl]manganese: A Source of Benzeneselenolatomanganese Derivatives of Diverse Nuclearity

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

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