Rhenium(I) Coordination Chemistry: Synthesis, Reactivity, and Electrochemistry of Terpyridyl Complexes

Helberg, Lisa E.; Barrera, Joseph; Sabat, Michal; Harman, W. Dean

doi:10.1021/ic00112a014

Cited by 31 publications

(49 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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“…1, [43][44][45][46][47] Despite the inability of polypyridal rhenium complexes to act as dearomatization agents, their alkene and carbonyl complexes provided a match to the electrochemical profiles of analogous osmium complexes (Table 1). 1, [43][44][45][46][47] These complexes also provide similar backdonation ability based on the IR stretches of their dinitrogen complexes.…”

mentioning

confidence: 99%

“…1, [43][44][45][46][47] These complexes also provide similar backdonation ability based on the IR stretches of their dinitrogen complexes. [20][21]45 These results demonstrated that despite the ability to mimic the electronic requirements of the {Os(NH3)5} 2+ fragment, sterics also play an important role in the dihapto-coordination of aromatic molecules.…”

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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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Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon–Bromine Bonds by Single‐Electron Transfer

Jiang¹,

Blacque²,

Fox³

et al. 2010

Chemistry A European J

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The five-coordinated Re(I) hydride complexes [Re(Br)(H)(NO)(PR(3))(2)] (R=Cy 1 a, iPr 1 b) were reacted with benzylbromide, thereby affording the 17-electron mononuclear Re(II) hydride complexes [Re(Br)(2)(H)(NO)(PR(3))(2)] (R=Cy 3 a, iPr 3 b), which were characterized by EPR, cyclic voltammetry, and magnetic susceptibility measurements. In the case of dibromomethane or bromoform, the reaction of 1 afforded Re(II) hydrides 3 in addition to Re(I) carbene hydrides [Re(=CHR(1))(Br)(H)(NO)(PR(3))(2)] (R(1)=H 4, Br 5; R=Cy a, iPr b) in which the hydride ligand is positioned cis to the carbene ligand. For comparison, the dihydrogen Re(I) dibromide complexes [Re(Br)(2)(NO)(PR(3))(2)(eta(2)-H(2))] (R=Cy 2 a, iPr 2 b) were reacted with allyl- or benzylbromide, thereby affording the monophosphine Re(II) complex salts [R(3)PCH(2)R'][Re(Br)(4)(NO)(PR(3))] (R'=-CH=CH(2) 6, Ph 7). The reduction of Re(II) complexes has also been examined. Complex 3 a or 3 b can be reduced by zinc to afford 1 a or 1 b in high yield. Under catalytic conditions, this reaction enables homocoupling of benzylbromide (turnover frequency (TOF): 3 a 150, 3 b 134 h(-1)) or allylbromide (TOF: 3 a 575, 3 b 562 h(-1)). The reaction of 6 a and 6 b with zinc in acetonitrile affords in good yields the monophosphine Re(I) complexes [Re(Br)(2)(NO)(MeCN)(2)(PR(3))] (R=Cy 8 a, iPr 8 b), which showed high catalytic activity toward highly selective dehydrogenative silylation of styrenes (maximum TOF of 61 h(-1)). Single-electron transfer (SET) mechanisms were proposed for all these transformations. The molecular structures of 3 a, 6 a, 6 b, 7 a, 7 b, and 8 a were established by single-crystal X-ray diffraction studies.

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Rhenium(I) Coordination Chemistry: Synthesis, Reactivity, and Electrochemistry of Terpyridyl Complexes

Cited by 31 publications

References 0 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

Development of 2nd Row Molybdenum Dearomatization Agents

Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon–Bromine Bonds by Single‐Electron Transfer

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