Synthesis and Reactivity of Molybdenum‐Dinitrogen Complexes Bearing PNN‐Type Pincer Ligand

Arashiba, Kazuya; Nakajima, Kazunari; Nishibayashi, Yoshiaki

doi:10.1002/zaac.201400117

Cited by 23 publications

(14 citation statements)

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“…More recently MoCl 3 (thf ) 3 was added to 25 Et to give the 25 Et MoCl 3 complex, which can be reduced with the Na-Hg amalgam, in the presence of PMe 3 or PMe 2 Ph and nitrogen, to the Mo(0) complexes 25 Et Mo(N 2 ) 2 PMe 3 and 25 Et Mo (N 2 ) 2 PMe 2 Ph, respectively. 41 The Mo(V) nitride complex (25 Et MoNCl) has also been reported. 42 This reflects a broadening interest in these PNN ligands and indicates that PNN ligands could be used with other metals as well.…”

Section: A Pnn Ligands and Complexesmentioning

confidence: 99%

Non-symmetric pincer ligands: complexes and applications in catalysis

2015

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Pincer ligands have become ubiquitous in organometallic chemistry and homogeneous catalysis. Recently, new varieties of pincer ligands with non-symmetrical backbones and/or ligating groups have been reported and their application in transition metal complexes has been exploited in a variety of catalytic transformations. This non-symmetric approach vastly increases the structural and electronic diversity of this class of ligand. This approach has proven beneficial in a variety of ways, such as the use of a single weakly coordinating moiety, which can dissociate and thereby create a vacant coordination site to increase the catalyst activity. Additionally, this provides further access to chiral ligands and complexes for asymmetric induction. This perspective highlights recent, important examples of non-symmetric pincer ligands, which feature aryl or pyridine backbones, and the synthesis and use of subsequent complexes in catalytic transformations, and discusses the future potential of this type of ligand system.

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Section: A Pnn Ligands and Complexesmentioning

confidence: 99%

Non-symmetric pincer ligands: complexes and applications in catalysis

2015

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“…This stands in stark contrast to the reactivity trends of the Chatt‐type complexes [M(N 2 ) 2 (PMe 2 Ph) 4 ],30 which showed high selectivity for ammonia formation mediated by tungsten complexes, and much higher activity than their molybdenum analogues. Substituting one of the phosphine donors of the PNP ligand with a diethyl amino group resulted in a lower ammonia yield after protonolysis of the molybdenum complex 58…”

Section: Groupmentioning

confidence: 99%

Reactivity of Dinitrogen Bound to Mid‐ and Late‐Transition‐Metal Centers

et al. 2015

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This review presents a comprehensive overview of the reactions of N 2 within the coordination sphere of transition metals of groups 6 to 9. Many of these metals mediate the reaction of N 2 with protons under reductive conditions, which can lead to the (catalytic) formation of ammonia or hydrazine, and the mechanisms of these reactions somewhat resemble the mode of action of nitrogenase enzymes. Alternatively, coordinated N 2 can react with carbon and silicon electrophiles and radicals to allow, for example, the catalytic formation of[a] Van '567 silylamines. Another approach in N 2 activation involves the homolytic splitting of dinitrogen to form intermediate nitrides in analogy to the Haber-Bosch process. Thus formed nitrides can undergo follow-up reactions with protons or carbon electrophiles. Molybdenum, tungsten, and iron reveal the richest chemistry of coordinated N 2 ; however, chromium, manganese, rhenium, osmium, and cobalt systems provide alternative pathways in the making and breaking of bonds on the dinitrogen molecule.Nitesh Khoenkhoen (1989) received his Bachelor of Science degree in chemistry at Utrecht University, The Netherlands, where he participated in undergraduate research under the supervision of Prof. Petra E. de Jongh in the area of inorganic chemistry and catalysis. After a short internship at the University of Amsterdam, he moved to the VU University Amsterdam, where he is currently a master's student in the laboratory of Professor Koop Lammertsma and is studying the generation of free phosphinidenes. Bas de Bruin (1971) did his PhD research at the RUN in Nijmegen (Prof. A. W. Gal, 1999). He did his postdoctoral research at the MPI für Bio-Anorganische Chemie in Mülheim a/d Ruhr (Prof. K. Wieghardt), after which he returned to the RUN as an assistant professor. In 2005, he moved to the University of Amsterdam (UvA, The Netherlands), where he was promoted to associate professor in 2008 and to full professor in 2013. He is involved in various research activities, including radical organometallic chemistry, EPR spectroscopy, olefin oxygenation, polymer synthesis, mechanistic studies, and computational catalysis with a focus on the development of new (bio-inspired) catalytic transformations. Joost N. H. Reek (1967) completed his PhD in Nijmegen with a thesis on supramolecular chemistry (Prof. Nolte). After a postdoctoral fellowship in Sydney Australia with Prof. Crossley, he joined the group of Prof. van Leeuwen at the University of Amsterdam (UvA, The Netherlands) as an assistant professor (1998), where he started research activities that focused on transition-metal catalysis. He was promoted to associate professor in 2003, and in 2006 he became full professor and elected member of the Young Royal Academy of Science. In 2009, he started a spin-off company (InCatT) to explore the commercial potential of new supramolecular strategies for combinatorial approaches in (asymmetric) catalysis. In 2013, he became the director of the Van 't Hoff Institute for Molecular Science. His current research ...

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“…In the case of PPh 2 , an additional donor ligand has to be added to stabilize the Mo 0 oxidation state (Scheme 43, top) 149 ,150 ,151 ,. Similar requirements are found for [PNN] ligands 152. On the other hand, with P(alkyl) 2 moieties,153 the Mo 0 complex can be stable in the absence of additional phosphine and several complexes featuring bridging end-on N 2 ligand have been synthesized which have proved relevant to N 2 functionalization in recent years (vide infra) (Scheme 43, middle) 154.…”

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confidence: 60%