Preparation of Rhenium(I) and Rhenium(II) Amine Dinitrogen Complexes and the Characterization of an Elongated Dihydrogen Species

Chin, R; Barrera, Joseph; Dubois, Raymond H.; Helberg, Lisa E.; Sabat, Michal; Bartucz, Tanya Y.; Lough, Alan J.; Morris, Robert H.; Harman, W. Dean

doi:10.1021/ic9700866

Cited by 47 publications

(41 citation statements)

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“…[46] We found that the [Re III Br(tacn) (CO) 3 ] 2+ complex (7) is the likely first redox reactions either from the corresponding Re(i) or Re(iii) complexes. This is especially true for coordination compounds [41][42][43][44][45] 2 ] complexes (Scheme 1). [40] These simple ligand substitution reactions are a rare feature for a mononuclear 17-electron rhenium complex.…”

Section: The Cis-[rementioning

confidence: 99%

“…[4] Thus, fewer than 50 articles comprise the entire literature of Re(ii) chemistry and these can be further reduced to 15 fundamental reports. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] The rhenium chemistry of this oxidation state is dominated by phosphorus ligands. A few notable exceptions are complexes of binding ligands such aromatic amines or isocyanides.…”

Section: Introductionmentioning

confidence: 99%

“…A few notable exceptions are complexes of binding ligands such aromatic amines or isocyanides. [12,14] The main routes for the synthesis of Re(ii) compounds involve oxidation of Re(i) or the reduction of Re(iii) complexes. Additionally, examples are known where Re(ii) species are formed via the cleavage of ReRe bonds of bimetallic units such as [Re 2 (NCCH 3 ) 10 ] 4+ .…”

Section: Introductionmentioning

confidence: 99%

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A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

Zobi

2010

Chimia

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Transition metal complexes of rhenium and technetium find wide application in nuclear medicine and the chemistry of these elements is still the focus of intense research efforts. For therapeutic and diagnostic applications, currently much attention is dedicated to the development of new targeting strategies aimed at appending the metal complexes to biological vectors (e.g. a peptide) for a site-specific delivery of the radio-nuclides. Advancements in radiopharmacy, however, will not only arise from the development of new targeted strategies but also from the exploration of the chemistry of these elements in their unusual oxidation states. In this respect the even number oxidation states of Re and Tc (i.e. +II, +IV and +VI) are relatively poorly understood. In particular, stable and substitutionally labile mononuclear 17-electron species of the elements (+II, d (5)) are a rarely encountered class of complexes. In this review we present our recent developments in the field of rhenium (II) chemistry with emphasis on the novel synthetic strategies we have recently introduced. We will also describe how the unique chemical and electronic properties of Re(II)-based complexes may provide a potentially new approach for applications in inorganic medicinal chemistry.

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Section: The Cis-[rementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

Zobi

2010

Chimia

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“…[15,16] As yet there are no reports in the literature of dicationic dihydrogen complexes of transition metals with the PF 3 ligand. Therefore, in continuation of our investigations on the heterolytic activation of molecular hydrogen we report here the first examples of dicationic dihydrogen complexes of iron and ruthenium with a trans-PF 3 ligand trans-[M(η 2 -H 2 )(PF 3 )(diphosphane) 2 ] 2ϩ (M ϭ Fe, diphosphane ϭ dppe; M ϭ Ru, diphosphane ϭ dppm, dppe).…”

Section: )(Pph 3 )(Pf 3 )(Dien)]mentioning

confidence: 99%

Synthesis and Characterization of the First Examples of Dicationic Dihydrogen Complexes of Iron and Ruthenium with the PF₃ Ligand

2004

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New dicationic dihydrogen complexes of the type trans‐[M(η2‐H2)(PF3)(diphosphane)2]2+ [M = Ru, diphosphane = dppm (Ph2PCH2PPh2); M = Fe, Ru, diphosphane = dppe (Ph2PCH2CH2PPh2)] have been prepared from the precursor hydrides trans‐[M(H)(PF3)(diphosphane)2]+ upon reaction with HOTf. In the case of dppm, in addition to the trans‐dihydrogen complex cis‐[Ru(η2‐H2)(PF3)(dppm)2]2+ was also obtained in the protonation reaction. The intact nature of the H−H bond in these derivatives has been established using the spin−lattice relaxation time measurements (short T1 values) and the large JH,D coupling constant of the H−D isotopomers. The H−H bond lengths and the stabilities of the dihydrogen complexes are discussed in terms of the π‐acidity of the PF3 ligand and compared with other systems possessing trans CO and CNH ligands. The trans‐[Ru(η2‐H2)(PF3)(dppe)2]2+ complex was found to be remarkably stable with respect to the loss of bound H2 for a period of about 16 h. The H−D isotopomer of this complex exhibits small temperature variations in the JH,D coupling constant. The X‐ray crystal structure of trans‐[Ru(H)(PF3)(dppm)2][BF4] has been determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…[48][49][50] Like the previously discussed polypyridal ligand set the new rhenium species also afforded a variety of dihapto-complexes (Scheme 3), with similar electronic properties. However, despite the success in once again reproducing the electronic requirements of the osmium system, η 2 -aromatic complexes remained elusive.…”

Section: +mentioning

confidence: 62%

Development of 2nd Row Molybdenum Dearomatization Agents

Shivokevich¹

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ii I am fortunate to have so many people to thank. I truly would not be here, having written all of the pages before you if it weren't for the huge amounts of love and support that I have received from so many along the way. Most of the people listed in this section know that I have a difficult time expressing my feelings. I will attempt to overcome that difficulty here and hopefully give a small amount of something back to all those who have contributed so much to me. I know that I will not do justice to the feelings that I have, but will try my best to express them here. With that in mind, know that as you read on that this was the most difficult, and time consuming part of my thesis to write. It is because I have been fortunate enough to come into contact with a great many wonderful people that any of the subsequent chapters exist; so to say that these acknowledgements are the foundation of my thesis would be an understatement.So here we go. I will start with those who have supported me from the start, my parents. My parents have always encouraged, nurtured, loved and supported me in any venture that I have undertaken. As teachers, they have shown me the importance of education in so many ways. As their way of life, in their professional lives, and also at home. They always stressed the importance of reading, but also looked to establish education in other less traditional ways. These have included travel, and along the way sparked my love of both history and the outdoors, which have continued to be passions of mine to this day. Through my parents I also learned a great deal about the world around me that was not covered in the classroom curriculum. Learning how to build and fix things from my Dad has been a skill that has helped me countless times throughout life, although it also came with the unfortunate side effect of having to constantly fix the rotovap. My Dad also instilled in me the time and money sinks of boating and woodworking, both of which have given me countless hours of joy, and a means of finding peace at stressful times in my life as an adult. In the classroom my parents taught me to iii appreciate all subjects, which I did (except for English class, I hate grammar as anyone at Dean's writing workshop could tell you). This eventually led me to chemistry, which astonished my parents. I went off to college and pursued chemistry, becoming more interested as classes progressed, although I still could not shake my humanities leaning, and ended up with degrees in both chemistry and history.My parents continued to give me support when I set off for Charlottesville. They helped in my apartment search and moving the large amount of stuff that I had accumulated. They then made several house hunting trips, and we drove circles around Charlottesville and the surrounding counties. When I finally bought my first home in the spring of my first year, they both used nearly all of their vacation time to come down and help me with the seemingly endless remodels. I never could have finished it without them. All ...

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Preparation of Rhenium(I) and Rhenium(II) Amine Dinitrogen Complexes and the Characterization of an Elongated Dihydrogen Species

Cited by 47 publications

References 27 publications

A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

Synthesis and Characterization of the First Examples of Dicationic Dihydrogen Complexes of Iron and Ruthenium with the PF₃ Ligand

Development of 2nd Row Molybdenum Dearomatization Agents

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Preparation of Rhenium(I) and Rhenium(II) Amine Dinitrogen Complexes and the Characterization of an Elongated Dihydrogen Species

Cited by 47 publications

References 27 publications

A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

Synthesis and Characterization of the First Examples of Dicationic Dihydrogen Complexes of Iron and Ruthenium with the PF3 Ligand

Development of 2nd Row Molybdenum Dearomatization Agents

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Product

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Synthesis and Characterization of the First Examples of Dicationic Dihydrogen Complexes of Iron and Ruthenium with the PF₃ Ligand