Quantum yields in photolysis of (diene)tricarbonyliron and bis(diene)carbonyliron complexes

Jaenicke, Ottmar; Kerber, Robert C.; Kirsch, Peer; Gustorf, E. A. Koerner Von; Rumin, René

doi:10.1016/s0022-328x(00)93429-6

Cited by 20 publications

(19 citation statements)

References 33 publications

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“…Concrete information on the underlying transitions is lacking, apart from the observation that the efficiency of both CO and diene photosubstitution decreases significantly on going from shorter to longer wavelengths. At 313 nm, for example, Φ CO = 0.16 and Φ diene = 0.015 were measured with trimethyl phosphite as the entering ligand . Thus, flash photolysis of 1 at λ = 308 nm, using the XeCl excimer laser routinely available in our experimental setup, seems appropriate for the present time-resolved IR spectroscopic study.…”

Section: Resultsmentioning

confidence: 95%

“…High yields of the latter compounds are accessible from photogenerated Fe(CO) 3 (η 4 -1,3-diene) by further CO photosubstitution occurring upon extended irradiation in the presence of excess diene. , Other photoinduced reactions of Fe(CO) 3 (η 4 -1,3-diene) complexes include CO/ 13 CO exchange, metal-assisted diene−olefin coupling, , and CO substitution by phosphine ligands yielding Fe(CO) 2 (η 4 -1,3-diene)(L) derivatives, , whereas replacement of the diene plays only a minor role …”

Section: Introductionmentioning

confidence: 99%

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A Novel Facet of Carbonyliron-Diene Photochemistry: The η⁴-s-transIsomer of the Classical Fe(CO)₃(η⁴-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods

et al. 2003

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The photolysis of Fe(CO)3(η4-s-cis-1,3-butadiene) (1) and Fe(CO)4(η2-1,3-butadiene) (2), formerly studied in low-temperature matrixes, is reexamined in cyclohexane solution at ambient temperature using time-resolved IR spectroscopy in the ν(CO) region. Flash photolysis of 2 (λexc = 308 nm) generates Fe(CO)3(η4-s-trans-1,3-butadiene) (5) as a transient product, which then rearranges to form the classical η4-s-cis-1,3-butadiene complex 1. Species 5, previously addressed as the coordinately unsaturated Fe(CO)3(η2-1,3-butadiene) (3), is also photogenerated from 1, in this case along with the very short-lived CO loss fragment Fe(CO)2(η4-1,3-butadiene) (τ < 4 μs under CO atmosphere). It decays by temperature-dependent first-order kinetics (τ = 13 ms at 25 °C; ΔH ⧧ = 17.3 kcal·mol-1) with nearly complete recovery of 1. According to density functional calculations at the BP86 level of theory, 5 resides in a distinct energy minimum, 20.3 kcal·mol-1 above 1 and separated from it by a barrier of 15.0 kcal·mol-1. Its computed structure involves a diene dihedral angle of 129°. Species 3 (with a diene dihedral angle of −150.1°), by contrast, is predicted to exist in a rather flat minimum, which makes it too short-lived for detection with our instrumentation. Flash photolysis of Fe(CO)5 generates the very short-lived (<1 μs) doubly unsaturated Fe(CO)3(solv) species in addition to the familiar Fe(CO)4(solv) fragment (τ = 10−15 μs), Fe2(CO)9 being the ultimate product in the absence of potential trapping agents other than CO. Deliberate contamination of the system with water gives rise to the formation of Fe(CO)4(H2O) as a longer lived transient (ca. 1 ms). In the presence of 1,3-butadiene, both 2 and 5 appear almost instantaneously. The latter decays, again in the millisecond time range, with formation of 1, thus providing clear evidence of a single-photon route from Fe(CO)5 to 1 in addition to the established two-photon sequence via the monosubstituted complex 2.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

A Novel Facet of Carbonyliron-Diene Photochemistry: The η⁴-s-transIsomer of the Classical Fe(CO)₃(η⁴-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods

et al. 2003

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“…Photosubstitution reactions of the tricarbonyliron fragment are of synthetic utility due to kinetic inertness of the Fe(CO) 3 group. Pioneering work by Von Gustorf and his group [ 511 ] demonstrated efficient CO substitution when Fe(CO) 3 -(1,3-diene) complexes were excited with ultraviolet radiation. A few new examples from the recent literature are reported next.…”

Section: Miscellaneous Recent Resultsmentioning

confidence: 99%

New chemical and stereochemical applications of organoiron complexes

Fatiadi

1991

J. RES. NATL. INST. STAN.

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The objective of this review is to provide a current overview of the rapidly developing chemistry of organometallic complexes and particularly organoiron complexes useful in asymmetric and stereoselective reactions. Also covered are stereoselective reactions of α, β-unsaturated acyl ligands bound to the chiral auxiliary [(η5-C5H5) Fe(CO)(PPh3)] and new applications of organoiron complexes in the synthesis of natural products. The mechanistic aspects and stabilizing effects of the Fe(CO)3 group for alkenes or conjugated dienes are discussed. A brief summary of recent work on the special role of iron in biological reactions is also included.

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“…Calculations using Ru(CO) 2 and Fe(PH 3 ) 2 or Fe(PH 3 )(CO) as ligands coordinated at the cyclobutadiene site showed rather small changes in the calculated gap. In terms of the chemistry of these systems, replacement of CO by phosphine is a facile process, and so synthetic realization of such materials containing derivatives of this type should not be difficult. Perhaps a diphosphinoethane ligand of the correct size could be used to link two adjacent metal atoms.…”

Section: The 44 Polymermentioning

confidence: 99%

Electronic Structure and Properties of Bunz' Polymers

Burdett

Mortara

1997

Chem. Mater.

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The Bunz polymers consist of n-membered rings of carbon atoms connected via n monoor diethynyl units (m ) 1, 2 respectively) to other such rings. Coordinated to the three-, four-, and five-membered rings are ML n units (L ) CO, Cp) which lead to 18-electron rule stability at each metal-organic center. The electronic band structures of the metal-free (often metallic) and metal-complexed (always insulating) materials are derived, and it is shown how the insulating polymer-M(CO) 3 systems may be converted to systems with small bandgaps by the loss of a CO group. Depending on the width of the conduction band, either small bandgap semiconductors, ferromagnetic metals or antiferromagnetic insulators are predicted. The properties of C 6 ML x polymers are also investigated (ML x ) NO, CO, C 3 H 3 + ). These consist of an ML x unit attached to a graphite sheet. Bending the MNO group converts the linear three-electron donor "NO + " unit into an "NO -" moiety and generation of a metal. By construction of polymers with specific arrangements of M(CO) 3 and MCp groups, interesting patterns of metallic and insulating units may be envisaged at the atomic level.

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Quantum yields in photolysis of (diene)tricarbonyliron and bis(diene)carbonyliron complexes

Cited by 20 publications

References 33 publications

A Novel Facet of Carbonyliron-Diene Photochemistry: The η⁴-s-transIsomer of the Classical Fe(CO)₃(η⁴-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods

A Novel Facet of Carbonyliron-Diene Photochemistry: The η⁴-s-transIsomer of the Classical Fe(CO)₃(η⁴-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods

New chemical and stereochemical applications of organoiron complexes

Electronic Structure and Properties of Bunz' Polymers

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Quantum yields in photolysis of (diene)tricarbonyliron and bis(diene)carbonyliron complexes

Cited by 20 publications

References 33 publications

A Novel Facet of Carbonyliron-Diene Photochemistry: The η4-s-transIsomer of the Classical Fe(CO)3(η4-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods

A Novel Facet of Carbonyliron-Diene Photochemistry: The η4-s-transIsomer of the Classical Fe(CO)3(η4-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods

New chemical and stereochemical applications of organoiron complexes

Electronic Structure and Properties of Bunz' Polymers

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Product

Resources

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A Novel Facet of Carbonyliron-Diene Photochemistry: The η⁴-s-transIsomer of the Classical Fe(CO)₃(η⁴-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods

A Novel Facet of Carbonyliron-Diene Photochemistry: The η⁴-s-transIsomer of the Classical Fe(CO)₃(η⁴-s-cis-1,3-butadiene) Discovered by Time-Resolved IR Spectroscopy and Theoretically Examined by Density Functional Methods