NDLI: Photoinduced N<sub>2</sub> loss as a route to long-lived organometallic alkane complexes: A time-resolved IR and NMR study

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Synthesis and antifreeze activity of fish antifreeze glycoproteins and their analogues

Photodissociation and photoelectron imaging of molecular ions: probing multisurface and multichannel dynamics

Total synthesis of all (−)-agelastatin alkaloids

Exploiting donor–acceptor interactions in aqueous dynamic combinatorial libraries: exploratory studies of simple systems

Site-specific photocatalytic splitting of methanol on TiO₂(110)

Dissecting tunicamycin biosynthesis by genome mining: cloning and heterologous expression of a minimal gene cluster

Highly enantioselective synthesis of 1,3-bis(hydroxymethyl)-2-oxindoles from unprotected oxindoles and formalin using a chiral Nd^III complex

Site-specific PEGylation of proteins by a Staudinger-phosphite reaction

A versatile, solvent-free methodology for the functionalisation of carbon nanotubes

A tangled web—interconnecting pathways to amorphadiene and the amorphene sesquiterpenes

Ambient temperature anion-dependent spin state switching observed in “mostly low spin” heteroleptic iron(ii) diimine complexes

Photoinduced N₂ loss as a route to long-lived organometallic alkane complexes: A time-resolved IR and NMR study

Frozen-solution magnetisation dynamics of hexanuclear oxime-based Mn^III Single-Molecule Magnets

Unified synthesis of enantiopure β²h, β³h and β^2,3-amino acids

X-ray snapshots for metalloporphyrin axial ligation

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Photoinduced N₂ loss as a route to long-lived organometallic alkane complexes: A time-resolved IR and NMR study

Content Provider	Royal Society of Chemistry (RSC)
Author	Anstey, Mitch Duckett, Simon B. Curley, John George, Michael W. Sun, Xue-Zhong Bergman, Robert G. Vollhardt, K. Peter C. Calladine, James A. Torres, Olga Ball, Graham E. Perutz, Robin N. Gilson, Amy I. Lawes, Douglas J.
Copyright Year	2010
Abstract	Photolysis of CpRe(CO)2(N2) in cyclopentane or 2,2-dimethylbutane with a UV lamp via a quartz fibre inserted into the NMR probe allows generation of CpRe(CO)2(cyclopentane) and CpRe(CO)2(2,2-dimethylbutane). The latter is observed in three isomeric forms according to the site of co-ordination to the rhenium. The major isomer, CpRe(CO)2(2,2-dimethylbutane-η2-C1,H1), exhibits a 1H NMR resonance for the co-ordinated hydrogen at δ = −2.19 with 1JC–H = 118 Hz. The photochemistry of Cp‡Re(CO)2(N2) (Cp‡ = η5-1,2-C5H3(tBu)2) in alkane solution is also reported. Two new organometallic alkane complexes, Cp‡Re(CO)2(alkane) (alkane = cyclopentane, n-heptane) have been characterized by IR spectroscopy following irradiation of Cp‡Re(CO)2(N2) and their rate constants for reaction with CO have been determined. The reaction with cyclopentane has also been studied by NMR spectroscopy at 190 K with in situ laser irradiation at 355 nm. Cp‡Re(CO)2(c-C5H10) is shown to exhibit the characteristic features of an alkane complex in the NMR spectrum, viz. a large isotopic shift of the 1H resonance at δ = −2.44 upon partial deuteration of the alkane (Δδ = 1.77 ppm), a large 1JC–H (114 Hz) and a large negative 13C chemical shift (δ = −33.8). We find no evidence for CO loss or agostic interactions of the t-butyl groups under these conditions. Cp‡Re(CO)2(alkane) has a slightly shorter lifetime (ca. 5x) than CpRe(CO)2(alkane) for a given alkane. Photolysis of CpRe(CO)2(N2) to form the organometallic alkane complex occurs with a much higher yield than for CpRe(CO)3. Efficient photo-ejection of N2 from Cp‡Re(CO)2(N2) is observed upon either 266 or 355 nm laser irradiation. A dinitrogen precursor allows for the use of longer wavelength irradiation and the generation of a higher concentration of the alkane complex following each laser pulse.
Starting Page	622
Ending Page	630
Page Count	9
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	1
Issue Number	5
Journal	Chemical Science
DOI	10.1039/c0sc00311e
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Infrared spectroscopy Isotopic shift Hydrogen Nuclear magnetic resonance spectroscopy Photodissociation CO Quartz Nitrogen Heptane Wavelength Isomer Chemical shift Organometallic chemistry Laser 2,2-Dimethylbutane Cyclopentane Nuclear magnetic resonance Rhenium Photochemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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Photoinduced N2 loss as a route to long-lived organometallic alkane complexes: A time-resolved IR and NMR study

Skeletal rearrangement of alkanes over Ir/Al₂O₃. Transformation of n-pentane, 2-methylbutane and 2,2-dimethylbutane

Dynamic NMR spectroscopy in studies of the kinetics of photoinduced chemical exchange in solutions

Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

A systematic approach to the generation of long-lived metal alkane complexes: combined IR and NMR study of $(Tp)Re(CO)_{2}(cyclopentane)$

The design, synthesis and photochemical study of a biomimetic cyclodextrin model of Photoactive Yellow Protein (PYP)

Photoinduced ligand isomerisation in a pyrazine-containing ruthenium polypyridyl complex

Crystal and molecular structures of Mo₂Cl₄(PMePh₂)₄ and Re₂Cl₄(PMePh₂)₄

Solution structural characterization of an array of nanoscale aqueous inorganic Ga_13−xIn_x (0 ≤x≤ 6) clusters by ¹H-NMR and QM computations

Photoinduced N₂ loss as a route to long-lived organometallic alkane complexes: A time-resolved IR and NMR study

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