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Polyhydrides of Platinum Group Metals: Nonclassical Interactions and Σ‑Bond Activation Reactions Miguel A

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Polyhydrides of Platinum Group Metals: Nonclassical Interactions and Σ‑Bond Activation Reactions Miguel A This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Review pubs.acs.org/CR Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ‑Bond Activation Reactions Miguel A. Esteruelas,* Ana M. Lopez,́ and Montserrat Olivań Departamento de Química Inorganica,́ Instituto de Síntesis Química y Catalisiś Homogeneá (ISQCH), Centro de Innovacioneń Química Avanzada (ORFEO−CINQA), Universidad de Zaragoza−CSIC, 50009 Zaragoza, Spain ABSTRACT: The preparation, structure, dynamic behavior in solution, and reactivity of polyhydride complexes of platinum group metals, described during the last three decades, are contextualized from both organometallic and coordination chemistry points of view. These compounds, which contain dihydrogen, elongated dihydrogen, compressed dihydride, and classical dihydride ligands promote the activation of B−H, C−H, Si−H, N−H, O−H, C−C, C−N, and C−F, among other σ-bonds. In this review, it is shown that, unlike other more mature areas, the chemistry of polyhydrides offers new exciting conceptual challenges and at the same time the possibility of interacting with other fields including the conversion and storage of regenerative energy, organic synthetic chemistry, drug design, and material science. This wide range of possible interactions foresees promising advances in the near future. CONTENTS 3.6.5. Si−H, Ge−H, and Sn−H Bond Activa- tions 8807 1. Introduction 8770 3.6.6. N−H and O−H Bond Activations 8810 2. Ruthenium 8772 3.6.7. Other σ-Bond Activations 8814 2.1. Phosphine Complexes 8772 4. Rhodium 8816 2.2. Complexes with Tetrapodal and Tripodal 5. Iridium 8817 Phosphine Ligands 8775 5.1. Phosphine Complexes 8817 2.3. Half Sandwich Compounds 8776 5.2. Complexes with Tripodal Phosphine Ligands 8821 2.4. Complexes with Tris(pyrazoyl)borate and 5.3. Half Sandwich Compounds 8821 Related Ligands 8777 5.4. Complexes with Tris(pyrazolyl)borate and 2.5. Complexes with Pincer Ligands 8778 Related Ligands 8822 2.6. Ruthenium-Polyhydride Complexes In- 5.5. Complexes with Pincer Ligands 8823 volved in σ-Bond Activation Reactions 8780 − 5.6. Iridium-Polyhydride Complexes Involved in 2.6.1. B H Bond Activation Reactions and σ-Bond Activation Reactions 8825 Related Processes 8780 5.6.1. B−H Bond Activation 8825 2.6.2. C−H Bond Activation 8782 − − 5.6.2. C H Bond Activation 8826 2.6.3. Si H Bond Activation 8784 5.6.3. Si−H Bond Activation 8828 2.6.4. N−H and O−H Bond Activations 8785 − σ 5.6.4. O H Bond Activation 8829 2.6.5. Other -Bond Activations 8786 6. Group 10 8829 3. Osmium 8787 7. Conclusion and Outlook 8830 3.1. Phosphine Complexes 8787 Author Information 8831 3.2. Complexes with Tetrapodal Phosphine Li- Corresponding Author 8831 gands 8792 Notes 8831 3.3. Half Sandwich Compounds 8792 Biographies 8831 3.4. Complexes with Tris(pyrazoyl)borate and Acknowledgments 8832 Related Ligands 8793 Dedication 8832 3.5. Complexes with Pincer Ligands 8794 References 8832 3.6. Osmium-Polyhydride Complexes Involved in σ-Bond Activation Reactions 8796 3.6.1. B−H Bond Activation Reactions 8796 3.6.2. Direct C−H Bond Activation 8798 3.6.3. Chelate-Assisted C−H Bond Activation 8800 − 3.6.4. C H Bond Activation of Imidazolium Special Issue: Metal Hydrides and Benzimidazolium Salts: Formation of NHC Complexes 8805 Received: February 4, 2016 Published: June 6, 2016 © 2016 American Chemical Society 8770 DOI: 10.1021/acs.chemrev.6b00080 Chem. Rev. 2016, 116, 8770−8847 Chemical Reviews Review 1. INTRODUCTION polyhydride skeleton and prevent position exchanges of these groups. In addition to the thermally activated site exchanges, Hydride is the ligand with the smallest number of valence some polyhydrides undergo quantum exchange coupling,21 electrons. It can only make single bonds to transition metal which manifests in the high field region of the 1H NMR spectra centers, which are among the strongest metal−ligand bonds.1 through large values of the observed H−H coupling constants Despite the strength of the M−H bonds, this ligand shows a (J ), which increase as the temperature increases. The great mobility and hydride site exchange is often observed.2 On obs phenomenon involves the exchange of the hydrogen nuclei. It the other hand, hydride has almost no steric influence. With its occurs by tunneling through a barrier between the two sides of uniquely small steric requirement, this ligand is ideal for the double-well potential,22 which is even lower than those achieving high coordination numbers. calculated for the hydrogen movements. For each temperature A major milestone for the understanding of the chemistry of − and a given hydrogen hydrogen separation (a), Jobs is transition metal hydride complexes was the discovery that the determined by eq 1, according to a two-dimensional harmonic hydrogen molecule can coordinate to a transition metal 23 3−6 oscillator model. Constant Jmag is the portion of Jobs due to the retaining almost intact the H−H bond. In contrast to the λ − − Fermi contact interaction, parameter is the hard sphere radius M H bond, the metal dihydrogen interaction is weak. Metal- of the hydrides, and ν describes the H−M−H vibrational wag dihydrogen and metal-dihydride forms are both parts of the mode that allows the movement along the H−H vector. They same redox equilibrium. Reducing metal centers favor the are characteristic for each compound and considered temper- oxidized dihydride form. However, oxidizing metal centers ature invariant. stabilize the reduced dihydrogen. The coordination enhances the acidity of the hydrogen molecule,7,8 which can undergo ⎡⎛ ⎞ ⎢ νa heterolytic cleavage9 and position exchange, through proton JJ=+2 ⎜ ⎟ obs mag ⎣⎢⎝ πλcoth[hkT ν /2 ]⎠ transfer, when a hydride coligand is also present in the complex. ⎧ ⎫⎤ In addition, the hydrogen atoms rapidly rotate around the −+2(πν222ma λ ) metal−dihydrogen axis. exp⎨ ⎬⎥ ⎩ ⎭⎦⎥ Other factors that have significantly contributed to the hhkTcoth[ν /2 ] (1) development of the field are the improvement of the quality of Saturated polyhydrides have the ability of losing molecular the characterization techniques, including X-ray and neutron − hydrogen to afford unsaturated species, which coordinate and diffractions,10 and NMR spectroscopy,11 13 and the availability subsequently activate σ-bonds, including B−H, C−H, Si−H, of more sophisticated programs and more potent computers for − − 14−18 N H, and O H bonds, among others. In this respect, DFT calculations, which are making possible the study of platinum group metals occupy a prominent place between − real molecules. Thus, today, it is possible to have a quite exact the metal elements.24 29 The activation of B−H bonds30,31 is a knowledge of the coordination polyhedra of the majority of the reaction of great interest concerning the borylation of organic − hydride complexes and the separation between the hydrogen molecules32 36 and the dehydrocoupling of ammonia-bor- − atoms bound to the metal center, in the solid state and in ane.37 39 The C−H bond activation is a classical issue in solution, and their mobility in solution. organometallics because of its connection with the functional- What do we understand by polyhydride complexes? We 40−47 fi ization of nonactivated organic substrates. The metal- de ne polyhydride complexes as compounds having enough mediated rupture of Si−H bonds is notable due to the hydrogen atoms bound to the metal center of a LnM fragment relevance of the M−SiR species in the hydrosilylation of to form at least two different types of ligands. These ligands can 3 fi unsaturated organic substrates, the direct synthesis of be classi ed in four types depending upon the separation chlorosilanes, and SiH/OH coupling.48 The N−Hbond between the coordinated hydrogens: (i) classical hydrides (>1.6 activation promoted by platinum group metals is a key step − Å), (ii) dihydrogen (0.8 1.0 Å), (iii) elongated dihydrogen in reactions of hydroamination of unsaturated organic − − (1.0 1.3 Å), and (iv) compressed dihydrides (1.3 1.6 Å). The molecules49 and for the use of ammonia in homogeneous distinction between elongated dihydrogen and compressed catalysis.50 The cleavage of O−H bonds is of potential dihydrides is formal, since for these species, the energy cost to relevance to metal-mediated solar-energy conversion routes.51 move the two hydrogens atoms between 1.00 and 1.60 Å is It is expected that water splitting driven by sunlight will −1 lower than 4 kcal mol (i.e., the energy of the complex is constitute a growing area of particular interest in the near practically independent of the separation between the hydrogen future.52 19 atoms). The main difference between them is the activation The coordination of a σ-E−E′ bond to a transition metal barrier for the combined rotation of both hydrogen atoms involves σ-donation from the σ-orbital of the coordinated bond − −1 around the M H2 axis, less than 8 kcal mol for the elongated − to empty orbitals of the metal and back bonding from the metal dihydrogen, and between 8 and 12 kcal mol 1 for the to the σ*(EE′) orbital. The activation toward homolysis or 20 compressed dihydrides. Nonclassical interactions are called heterolysis of the coordinated bond depends on the electronic those that occur around the metal coordination sphere, nature of the metal center. Nucleophilic metal centers enhance between hydrogen atoms separated by less than 1.6 Å. the back-donation, resulting in the homolytic addition of E−E′ A noticeable feature of polyhydride complexes is the to the metal. On the other hand, electrophilic metal centers combined movements of the hydrogen atoms bound to the increase the σ-donation to the metal, promoting the heterolytic metal center, in agreement with the mobility of hydride and cleavage of the E−E′ bond.
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