Photochemistry of (.eta.5-C5H5)2Fe2(CO)4 and related complexes in rigid matrixes at low temperature: loss of carbon monoxide from the trans isomer to yield triply CO-bridged species

Hepp, Aloysius F.; Blaha, Josephine Paw; Lewis, Claudia; Wrighton, Mark S.

doi:10.1021/om00079a031

Cited by 123 publications

(78 citation statements)

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“…The global minimum was found to be the triplet-state triply bridged structure Cp 2 Mn 2 (µ-NO) 2 (µ-CO) (IIa) ( Figure 3 and Table 2), which is isoelectronic with the known [37][38][39] Cp 2 Fe 2 (µ-CO) 3 . The Mn=Mn distance in IIa of 2.313 Å (B3LYP) or 2.294 Å (BP86) is very similar to the experimental Fe=Fe distance of 2.265 Å in Cp 2 Fe 2 (µ-CO) 3 and corresponds to a σ + 2 ⁄ 2 π triplet double bond similar to the double bond in isolated dioxygen.…”

Section: Cp 2 Mn 2 (No) 2 (Co)mentioning

confidence: 98%

(Cyclopentadienyl)nitrosylmanganese Compounds: The Original Molecules Containing Bridging Nitrosyl Groups

et al. 2009

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The (cyclopentadienyl)nitrosylmanganese derivatives Cp2Mn2(NO)2(CO)n (n = 2, 1, 0), Cp2Mn2(NO)3X (X = NO2, ‐C5H5), CpMn(NO)2, Cp2Mn2(NO)4, and Cp3Mn3(NO)4 have been investigated by using density functional theory. Six structures are found for Cp2Mn2(NO)2(CO)2 with various combinations of terminal and bridging carbonyl and nitrosyl groups within ca. 3 kcal/mol of each other indicating a highly fluxional system. A triplet‐state triply bridged structure is predicted to be the global minimum for Cp2Mn2(NO)2(CO), just as it is for the isoelectronic Cp2Fe2(CO)3. For Cp2Mn2(NO)2 a doubly bridged triplet structure is predicted to lie ca. 30 kcal/mol below the corresponding singlet structure, unlike the isoelectronic Cp2Fe2(CO)2. The structures predicted for Cp2Mn(µ‐NO)2(NO)X (X = NO2 and η1‐C5H5) and Cp3Mn3(µ‐NO)3(µ3‐NO) are close to the experimentally known structures. The monomer CpMn(NO)2, with a favorable 18‐electron configuration for the manganese atom, is predicted to be unstable with respect to dimerization to Cp2Mn2(µ‐NO)2(NO)2, for which two structures are found of similar energy. One Cp2Mn2(µ‐NO)2(NO)2 structure has a non‐bonding Mn···Mn distance of ca. 3.1 Å and linear terminal MnNO units, whereas the other Cp2Mn2(µ‐NO)2(NO)2 structure has a single‐bond Mn–Mn distance of ca. 2.5 Å and bent terminal MnNO units. In Cp2Mn(µ‐NO)2(NO)(η1‐Cp) the Mn2(µ‐NO)2 unit is unsymmetrical, with significantly different (by ca. 0.2 Å) Mn–N bond lengths to each side. However, in Cp2Mn2(NO)2(CO)n (n = 2, 1, 0) and Cp2Mn2(µ‐NO)2(NO)2 the Mn2(µ‐NO)2 units are symmetrical, with essentially the same Mn–N bond lengths to both sides. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Cp 2 Mn 2 (No) 2 (Co)mentioning

confidence: 98%

(Cyclopentadienyl)nitrosylmanganese Compounds: The Original Molecules Containing Bridging Nitrosyl Groups

et al. 2009

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“…Several positive-going peaks appear in Figure 5.3 that are assigned to CO-loss products based on literature values [139,193,[196][197][198]. In both neat n-hexane and phosphite solutions, a peak appears at ca.…”

Section: Dynamics Of Co-loss Productsmentioning

confidence: 86%

“…1823 cm -1 which is assigned to the bridging CO stretching mode of the COloss species 3 Cp 2 Fe 2 (µ-CO) 3 in a triplet spin state. The identity and spin state of this species has been definitively established [196][197][198]. This absorption grows in with a time constant of 22 ± 1 ps in neat n-hexane, 22 ± 1 ps in 2.0 M P(OMe) 3 , and 20 ± 1 ps in 300 mM P(OMe) 3 .…”

Section: Dynamics Of Co-loss Productsmentioning

confidence: 89%

Investigation of organometallic reaction mechanisms with one and two dimensional vibrational spectroscopy

Cahoon

2008

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“…The three optimized trans-C 8 H 6 Fe 2 (CO) 4 structures. 2 ⁄ 2 π type with one σ "full bond" and two orthogonal π "half-bonds," similar to the double bonds in triplet dioxygen or the organometallic [56] (η 5 -Me 5 C 5 ) 2 Fe 2 (μ-CO) 3 . The triplet spin state of 4T-2 arises from the unpaired single electrons in each of the two π "half-bonds."…”

Section: H 6 Fe 2 (Co)mentioning

confidence: 97%

Binuclear Pentalene Iron Carbonyl Complexes

Feng

Sun

et al. 2011

Eur J Inorg Chem

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The bicyclic hydrocarbon pentalene, although unstable in the free state, forms a stable iron carbonyl derivative cis‐(η5,η5‐C8H6)Fe2(CO)4(μ‐CO). In this connection, the series of binuclear pentalene iron carbonyl derivatives C8H6Fe2(CO)n (n = 7, 6, 5, 4) have been investigated by density functional theory. The lowest energy C8H6Fe2(CO)6 structure is predicted to be trans‐(η5,η5‐C8H6)Fe2(CO)6 without an iron–iron bond. However, a cis‐(η5,η1‐C8H6)Fe2(CO)6 structure with an uncomplexed pentalene C=C double bond and a formal Fe–Fe bond of length 2.646 Å (BP86) lies only ca. 3 kcal/mol above this global minimum. The CO dissociation energy of C8H6Fe2(CO)6 to give C8H6Fe2(CO)5 is predicted to be only ca. 12 kcal/mol, explaining the formation of C8H6Fe2(CO)5 rather than C8H6Fe2(CO)6 in reactions of dihydropentalene with iron carbonyls. In addition, the experimentally known cis‐(η5,η5‐C8H6)Fe2(CO)4(μ‐CO) structure is found to be the lowest energy C8H6Fe2(CO)5 structure by more than 25 kcal/mol (BP86). For the tetracarbonyl two triplet and two singlet cis‐C8H6Fe2(CO)4 structures lie within 7 kcal/mol of each other (BP86) with the triplet structures being of slightly lower energies. The singlet C8H6Fe2(CO)4 structure is predicted to be thermodynamically unfavorable with respect to disproportionation into C8H6Fe2(CO)5 + C8H6Fe2(CO)3.

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Photochemistry of (.eta.5-C5H5)2Fe2(CO)4 and related complexes in rigid matrixes at low temperature: loss of carbon monoxide from the trans isomer to yield triply CO-bridged species

Cited by 123 publications

References 1 publication

(Cyclopentadienyl)nitrosylmanganese Compounds: The Original Molecules Containing Bridging Nitrosyl Groups

(Cyclopentadienyl)nitrosylmanganese Compounds: The Original Molecules Containing Bridging Nitrosyl Groups

Investigation of organometallic reaction mechanisms with one and two dimensional vibrational spectroscopy

Binuclear Pentalene Iron Carbonyl Complexes

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