Spectroscopic evidence for the formation of tri-µ-carbonyl-bis-[(η⁵-cyclopentadienyl)iron] on photolysis of bis[(dicarbonyl)(η⁵-cyclopentadienyl)iron] in low temperature matrices

Abstract

Photolysis of [((~5-C5H,)Fe(CO)2}2] in CH4 (1 2 K) and polyvinyl chloride film (12-77 K) matrices leads to the formation of a novel species proposed, on the basis of i.r. evidence including I3CO enrichment and u.v.visible spectra, to be the CO-bridged dimerA recent flash photolysis study1 of the photochemistry of [ ((q5-C5H5)Fe(CO), >,I (1) provided evidence for two distinct

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

“…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.…”

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

“…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 .…”

“…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.…”

Structure, Spectroscopy and Photochemistry of the [M(η5-C5H5)(CO)2]2 Complexes (M=Fe, Ru)

“…The alkyne coordination, leading to formation of a transient [Cp 2 Fe 2 (CO) 3 (RCϵCR)] species, followed by intramolecular transformations, was also reported [51]. The nature of the [Cp 2 Fe 2 (CO) 3 ] intermediate has been discussed in the literature and was postulated to be triply [52][53][54][55][56][57][58], doubly [59] or singly CO-bridged [59]. Recently the photogenerated CO-loss intermediate was studied by time-resolved IR spectroscopy and its triply bridged structure was proved [60].…”