The X-ray photoelectron spectra of inorganic molecules

Tisley, D. G.; Walton, Richard A.

doi:10.1016/0022-2860(73)85181-6

Cited by 26 publications

(6 citation statements)

References 23 publications

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“…Extensive Re 4f and Mo 3d binding energy data are available for quadruply-bonded dirhenium [403][404][405][406][407] and dimolybdenum 408,409 complexes. It was suggested 410 on the basis of Mo 3d XPS studies that Mo-silica catalysts prepared from Mo 2 (O 2 CR) 4 may have different metal-support interactions from other Mo catalysts.…”

Section: X-ray Spectra Exafs and Xpsmentioning

confidence: 99%

Physical, Spectroscopic and Theoretical Results

Cotton

2005

Multiple Bonds Between Metal Atoms

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Structural Correlations Bond orders and bond lengthsThroughout the preceding chapters of this book we have reported and in some cases discussed the lengths of the multiple bonds between metal atoms. We have reported in tabular form most of the M-M distances that have been determined crystallographically. It is now time to make some general comments on these distances in relation to our understanding of the M-M bonds.It is a general qualitative rule in chemistry that bond lengths and bond orders are inversely related. In some limited areas, particularly with the fi rst-row elements carbon, nitrogen, and oxygen, quantitative relationships expressing bond length as a single-valued function of bond order are well known. However, these quantitative relationships are based heavily on faith, as well as fact. Bond lengths are facts; bond orders are not. In the process of inferring a bond order from a bond length one is often getting out no more than what was put in to begin with.We shall not further digress into a discussion of the philosophical ambiguities of these quantitative bond order-bond length correlations because they have proven to be useful, within their own sphere of application. However, there is no a priori reason to expect that similar procedures will (or will not!) work in the very different realm of metal-to-metal bonds. Experience is the only test, and experience thus far has shown that M-M bonds cannot usefully be treated in such a way.In the realm of M-M bonds it is best to invoke only a qualitative inverse relationship between bond order and bond length and to defi ne bond order only in a qualitative or ordinal way. In this book we have used the term M-M bond order only to indicate how many electron pairs are believed, on the basis of essentially qualitative considerations, to play a signifi cant part in holding the pair of metal atoms together. We condemn as foolish and hopeless any effort to associate a unique, precise, quantitative bond order with each and every M-M internuclear distance.In principle, M-M bond lengths, like others, should be amenable to treatment by the method of molecular mechanics, and some efforts [1][2][3][4] (hampered by a dearth of necessary experimental data) to do this have been reported. In general the results are encouraging and can account for

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Section: X-ray Spectra Exafs and Xpsmentioning

confidence: 99%

Physical, Spectroscopic and Theoretical Results

Cotton

2005

Multiple Bonds Between Metal Atoms

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“…As noted in the Introduction, in view of the interest in supported rhenium catalysts, it is necessary to know the binding energy (BE) values of unsupported compounds (in particular, the oxides) having different oxidation numbers (ON). The only extensive collection on rhenium compounds available in the literature refers to complexes [24], which are notably different in the nature of the bonds from those in rhenium oxides. The published data do not allow a clear picture to be drawn of the BE values vs ON.…”

Section: Xps D a T A A N D Be Values Of Rhenium Compoundsmentioning

confidence: 99%

Photoelectron spectroscopy (XPS) and thermogravimetry (TG) of pure and supported rhenium oxides 1. Pure rhenium compounds

Cimino¹,

Angelis

Gazzoli³

et al. 1980

Zeitschrift anorg allge chemie

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To investigate the interaction of rhenium with several supports, a preliminary study on pure rhenium compounds has been carried out in order to achieve a better understanding of their surface chemical properties. To this end X‐ray photoelectron spectroscopy (XPS) and thermogravimetry (TG) methods have been applied. The results show that metallic rhenium, ReO2 and ReO3 are covered with Re(VII). By heating in H2, NH4ReO4 and rhenium oxides are reduced to metallic rhenium in different temperature ranges. In the case of Re2O7 a spillover effect has been found when platinum is present. For ReO3 and ReO2 a morphological model has been described on the basis of combined XPS, TG and surface area measurements. The binding energy values of the different rhenium oxidation states have been assessed and their variation with the oxidation number briefly discussed.

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“…24a If bipy or phen are added to these solutions, the complexes L 2 ClReO 3 (L 2 ) bipy, phen) precipitate in high yield, revealing the intermediate formation of ClReO 3 . 27 However, in spite of their interest for the characterization of the XReO 3 complexes, all the methods named so far, have their practical value limited by the difficult synthesis and handling of all XReO 3 complexes (X ) F, Cl, Br) or by the use of strongly coordinating solvents and ligands. Furthermore, the preparation of other pseudohalide derivatives was difficult to envisage by such methods.…”

Section: Introductionmentioning

confidence: 99%

Rhenium(VII) Oxo and Imido Complexes: Synthesis, Structures, and Applications

1997

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ContentsI. Introduction 3197 II. LReO 3 Compounds and Derivatives 3199 A. Inorganic XReO 3 Compounds and Derivatives 3199 1. Dirhenium Heptaoxide, Re 2 O 7 , and Derivatives 3199 2. Halides and Pseudohalides of Type XReO 3 and Their Adducts 3200 3. R 3 EOReO 3 Compounds and Their Adducts (E ) C, Si, Sn, Ge, Sn, Pb) 3202 4. The Amido R 2 NReO 3 , the Phosphiniminato Complexes, and Their Adducts 3204 5. The Carboxylato Complexes (RCOO)-ReO 3 and Their Adducts 3204 6. The [L 3 ReO 3 ] + and [L 3 ReO 3 ] Complexes 3205 7. Miscellaneous Inorganic LReO 3 Derivatives 3206 8. Structural and Spectroscopic Characterization 3206 9. Reactions of Re 2 O 7 and XReO 3 Compounds 3208 B. Organic RReO 3 Compounds and Derivatives 3209 1. The Alkyl RReO 3 Derivatives 3209 2. The Methyl(vinyl)ReO 3 Complex 3212 3. Allyl, Benzyl, and Pseudoallylic Compounds 3212 4. The Alkinyl RReO 3 Derivatives 3212 5. The Aryl Derivatives 3213 6. The Cyclopentadienyl Derivatives 3213 7. The Indenyl Derivative 3214 8. Structural and Spectroscopic Characterization 3215 9. Reactions of Organic RReO 3 Compounds 3220 10. Applications 3223 III. The L 3 ReO 2 Compounds and Derivatives 3230 A. Inorganic X 3 ReO 2 Derivatives 3230 B. Organic and Mixed Derivatives 3231 IV. The L 4 Re 2 O 5 Compounds and Derivatives 3234 V. The L 5 ReO Compounds and Derivatives 3234 VI. The Re(VII) Imido Compounds and Derivatives 3234 A. The Inorganic XRe(NR) 3 Derivatives 3235 B. The Organic RRe(NR) 3 Derivatives 3236 C. The Inorganic X 3 Re(NR) 2 Derivatives 3236 D. The Organic R 3 Re(NR) 2 Derivatives 3237 E. Miscellaneous Polynuclear and Mixed Imido and Oxo−Imido Derivatives 3238 F. The X 5 Re(NR) Derivatives 3238 G. Reactions of XRe(NR) 3 Complexes 3238 H. Reactions of X 3 Re(NR) 2 and Derivatives 3239 1. The Imido−Alkyne XR(NAr) x (η 2 -C 2 R 2 ) 3-x Complexes 3239 2. The Imido−Alkylidene and Imido−Alkylidyne Complexes 3240 I. Structural Studies 3241 VII. Conclusions 3243 VIII. Abbreviations 3243 IX. Acknowledgments 3243 X. References 3243 3197

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The X-ray photoelectron spectra of inorganic molecules

Cited by 26 publications

References 23 publications

Physical, Spectroscopic and Theoretical Results

Physical, Spectroscopic and Theoretical Results

Photoelectron spectroscopy (XPS) and thermogravimetry (TG) of pure and supported rhenium oxides 1. Pure rhenium compounds

Rhenium(VII) Oxo and Imido Complexes: Synthesis, Structures, and Applications

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