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Nuclear magnetic resonance measurements confirm that, as expected, the mer isomer of tris(β-diketonato) cobalt(III) complexes is more stable (mer isomers are more stable because they are less affected by steric hindrance and they have lower dipoles). An excess of the mer isomer or only the mer isomer is experimentally observed. The existence of both fac and mer isomers is predicted by density functional theory calculations. At room temperature, the nuclear magnetic resonance peaks of phenyl-containing mer complexes are broad due to the intermediate rotation of bulky phenyl groups resulting in only the average orientation of the non-equivalent protons in the mer complexes. However, upon heating to 55°C (thus speeding up the rotation) or cooling to −50°C (slowing down the rotation), this broad peak is resolved into three sets of carbon peaks appearing in the 13C NMR spectrum, as well as splitting of the ¹H NMR peaks for the non-equivalent protons in the mer isomer. In solid-state 13C NMR the aromatic rings do not rotate, resulting in the splitting of all the 13C NMR peaks. Two sets of well-defined peaks are observed for the fluorine-containing compound [Co(CF3COCHCOCPh)3] in both the 13C and 19F NMR spectra, indicating that both the fac and mer isomers are present with a ratio of fac:mer = 0.1:1. The X-ray photoelectron spectroscopy measured binding energy of the Co 2p3/2 photoelectron lines are influenced by the subtle electronic (electron-donating or electron-withdrawing) properties of the R groups on the β-diketonato ligands. Various relationships are established between the binding energy of Co 2p3/2 and several physical and density functional theory–calculated properties, confirming good electronic communication (the measurable electronic effect that a molecular fragment has on the physical properties of another molecular fragment in the molecule) of the substituent groups through the pseudo aromatic system of the β-diketonato backbones to the metal. [ABSTRACT FROM AUTHOR]

p-Cresol as additive to the Grubbs second generation catalyst (GII) allows the cross-metathesis of acrylates with prop-1-en-1-ylbenzenes under conditions that only give the prop-1-en-1-ylbenzene self-metathesis product in the absence of cresol. NMR and IR spectroscopy, MALDI-TOF MS and XPS supported the formation of a ruthenium benzylidene with hydrogen bonds between p-cresol and the chloride ligands of GII. XPS furthermore confirmed p-cresol to increase the binding energies of the GII Ru 3d5/2, 3d3/2, 3p3/2 and 3p1/2 photoelectron lines, whereas 1H NMR spectroscopy indicated the carbene carbon and hydrogen to be shielded. It is thus postulated that p-cresol allows for more facile interaction between electron-deficient compounds and the ruthenium benzylidene by decreasing the electron density on the metal center and increasing the electron density on the carbene. [ABSTRACT FROM AUTHOR]

A systematic analysis of the XPS Fe 2p 3/2 core-level photoelectron lines and their satellite structures gave insight into the electronic properties of a series of ferrocenyl-containing chalcones with the structure Fc CO CH CH C 6 H 4 R, where R is in the para -position on the phenyl ring and R OCH 3 ( 1 ), CH 3 ( 2 ), C 6 H 5 ( 3 ), t Bu ( 4 ), H ( 5 ), Br ( 6 ) and CF 3 ( 7 ). A V-shaped correlations obtained between the binding energy of the Fe 2p 3/2 photoelectron line and Hammett constants (σ R ) of the R-groups as well as the oxidation potential of the Fe II /Fe III couple, E pa , indicates that there are different modes of zwitterion formation, of electron-donating and electron-withdrawing R-substituents, after photoemission of an electron during the XPS measurements. The intensity of the satellite peak ( I ratio ) within the substructure of the photoelectron line is an indication of the amount of charge being transfer from the donor (ferrocenyl-fragment) to the acceptor fragments. The link between the Gordy group electronegativities, λ R , and I ratio show that more charge is being transfer from Fc in chalcone with more electron withdrawing R-groups. During electron transfer processes (like electrochemical oxidation or photoemission) the chalcone undergoes inner-sphere reorganisation to compensate for the positively charged species which is formed. The I ratio is also an indication of the degree of inner-sphere reorganisation, while the carbonyl stretching frequency ( v CO as measured by ATR FTIR) is a measure of the amount of energy of required for this inner-sphere reorganisation. The link between I ratio and v CO showed that as the degree of inner-sphere reorganisation increases, more energy is required for this inner-sphere reorganisation. [ABSTRACT FROM AUTHOR]

[Display omitted] Three different classes of ferrocenyl-containing β-keto compounds Fc-CO-CH 2 -CO-R were synthesised to obtain two β-diketones with R = CH 3, 3 , and R = Fc (ferrocenyl = FeII(C 5 H 5)(C 5 H 4)), 4 , a β-ketoester, 5 , with R = OEt and a β-ketoamide, 6 , with R = NH 2. The β-diketones exhibited keto ⇌ enol tautomerization with the enol form Fc-CO-CH=C(OH)-R as the dominant isomer. Both the β-ketoester and β-ketoamide primarily existed in the keto form. FTIR and 1H NMR measurements could distinguish between keto and enol isomers. Dilute CHCl 3 solutions of 3 and 4 exhibited FTIR ѵ C=O keto vibrations between 1627 and 1712 cm−1 and ѵ C=O enol vibrations between 1590 and 1660 cm−1. X-ray photoelectron spectroscopic (XPS) measurements showed keto isomer Fe 2p 3/2 photoelectron lines at smaller binding energies than enol isomers. Significantly lower calculated molecular energies of the keto form of the β-ketoester 5 and β-ketoamide 6 utilising the Gaussian09 suite of programs at the B3LYP (uB3LYP for open-shell species), confirmed that 5 and 6 almost exclusively exists in the keto conformation. Cyclic voltammetry also distinguished between keto and enol isomers, and it was found that the electrochemical reversible ferrocenyl formal oxidation potential, E °ꞌ, of keto isomers of compounds can be estimated with the equation E °ꞌ keto = 170.99χ R –57.57 where χ R is the group electronegativities of R in FcCOCH 2 COR. This result complements earlier research that enables calculation of the ferrocenyl formal oxidation potentials of enol isomers of β-diketones. Computational studies further showed that the HOMO orbitals of 3 – 6 is exclusively on the Fe centre and computed Mulliken spin densities on the d xy orbital of the oxidised iron species approached 1 e−. [ABSTRACT FROM AUTHOR]

In methanol solutions, [Rh(FcCOCHCOR)(CO)(PPh 3)] and [Rh(FcCOCHCOR)(CO) 2 ] complexes do not undergo substitution or oxidative addition by MeOH. In contrast, when the same compounds are spin-coated on (OH)-capped silicon wafers, XPS measurements showed that, in the solid state, both ligand substitution and oxidative addition by Si-OH functionalities occur. Rh XPS binding energies are linearly related to RhI oxidation potentials and group electronegativities of the R-groups (CF 3 , CH 3 , phenyl and ferrocenyl). [Display omitted] A series of rhodium β-diketonato complexes [Rh(FcCOCHCOR)(CO) 2 ] and [Rh(FcCOCHCOR)(CO)(PPh 3)] with R = CF 3 , CH 3 , Ph = C 6 H 5 and Fc (ferrocenyl = FeII(C 5 H 5)(C 5 H 4)) were spin-coated on two-dimensional silanol-functionalised silicon wafers. Chemical reactions were observed that do not occur in ethanol solutions. Si-OH fragments on the wafers substituted ligands and oxidatively added to the Rh(I) centres. A multitude of different surface species could be identified with X-ray photoelectron spectroscopy (XPS). These included the parent spin-coated rhodium(I) complexes and rhodium(I) species that resulted from β-diketonato displacement from parent rhodium complexes by surface silanol OH's to generate [wafer-(O) 2 -Rh-(CO) 2 ]⊝ and [wafer-(O) 2 -Rh-(CO)(PPh 3)]⊝ units. Several RhIII surface species that inter alia resulted from oxidative addition of surface Si-OH groups to surface-coordinated RhI core atoms were also identified. Efficacy of β-diketonato ligand substitution by the silanol surfaces is a kinetically driven process and can be related to the rate of solution-phase β-diketonato substitution by 1,10-phenanthroline from parent [Rh(FcCOCHCOR)(CO) 2 ] and [Rh(FcCOCHCOR)(CO)(PPh 3)] complexes. The binding energies of the RhI and RhIII 3 d 5/2 photoelectron lines were found to be functions of Gordy scale R-group electronegativities and they are also linearly related to electrochemically determined RhI oxidation potentials. [ABSTRACT FROM AUTHOR]

Ethoxy chromium (0) Fischer carbene pentacarbonyl complexes [(CO) 5 CrC(OEt)R]; R = 2-thienyl ( 1 ), 2-furyl ( 2 ) were covalently anchored onto aminopropyltrimethoxysilane-functionalized silicon-wafers to form Cr-grafted Si-wafers S1 and S2 that were characterized by X-ray photoelectron spectroscopy (XPS). X-ray photoelectron spectroscopy determined that binding energy of the Cr 2p 3/2 photoelectron line of the thienyl-containing complexes were smaller than that of the furyl-containing complexes. The binding energy of the Cr 2p 3/2 photoelectron line of the ethoxycarbene complexes was smaller than that of aminocarbenes. The binding energy of the Cr 2p 3/2 photoelectron line of the Cr-grafted Si-wafers were ca. 1 eV higher than that of the related aminocarbenes. A 25–33% anchoring of the Cr-complexes 1 and 2 on the aminopropyltrimethoxysilane-functionalized silicon-wafers was achieved. [ABSTRACT FROM AUTHOR]

Surface-hydroxylated silicon wafers, 8, were reacted with 3-aminopropyltrimethoxysilane, 9, to create wafers with amine-functionalized surfaces, 10. The metallocenylaldehydes FcCHO, 1 (Fc = ferrocenyl = FeII(C5H5)(C5H4)), RcCHO, 2 (Rc = ruthenocenyl = RuII(C5H5)(C5H4)), and OcCHO, 3 (Oc = osmocenyl = OsII(C5H5)(C5H4)) as well as the carboxylic acids FcCOOH, 4, RcCOOH, 5, OcCOOH, 6, and Cc+COOH·PF6 −, 7 (Cc+ = cationic cobaltocenium = [CoIII(C5H5)(C5H4)]+), were reacted with 10 to covalently anchor the metallocenes on the wafers either via an imine (–CH N–) or amide (–NHCO–) bond. The aldehydes were anchored more effectively than the carboxylic acids. Binding energies of all important atoms in all seven systems were determined by XPS measurements. Metal binding energies of the amide-bonded metallocenes were consistently larger (up to 0.6 eV) than those of the imine-anchored systems. AFM and SEM measurements showed that the covalently anchored metallocenes aggregate into nano-islets of diameter between 40 and 100 nm depending on the metallocene and type of anchoring bond. Up to seven additional layers of unreacted metallocenylaldehyde or -acid further stacked on top of the main layer of metallocene to form each islet. These additional layers of metallocene of each islet are stabilized by a large network of secondary and/or tertiary bonding forces. The main film surfaces have average thicknesses ranging between 2 and 6 nm, while film roughness, which is mostly associated with the islets, was with one exception (that of the Oc–CONH– surface 14) between 17% and 68% of the film thickness. The crystal structures for OcCHO, 3, and Cc+COOH·PF6 −, 7, was determined and the observed tertiary and secondary intermolecular interactions between independent molecules explains the formation of the nano-islets of each metallocene when anchored onto the aminated silicon wafers. [ABSTRACT FROM AUTHOR]