Analyses of <i>Anionic </i>Cu(I) Complexes <i>via</i> Electrospray Mass Spectrometry

Lipshutz, Bruce H.; Stevens, Kirk L.; James, and Brian; Pavlovich, J.; Snyder, b James P.

doi:10.1021/ja960182q

Cited by 36 publications

(17 citation statements)

References 32 publications

(21 reference statements)

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“…[72b, 92] With the aid of 13 C, 6 Li, and 15 N NMR data, [93,94] Bertz et al pointed out that cyanide is not attached to copper(i) in the Lipshutz mix, and started the controversy. [95] Physical measurements by Penner-Hahn and co-workers [96,97] and Lipshutz et al, [98] and theoretical studies by the groups of Snyder, [99] and PennerHahn and Frenking [97] contributed much to the discussion. All of the recent crystallographic data for the cyanocuprates of ªhigher order stoichiometryº reported by Boche et al [100] and van Koten and co-workers [101] indicated that the cyanide anion is coordinated to lithium and not to copper.…”

Section: Organocopper Chemistrymentioning

confidence: 99%

Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry

Nakamura

Mori

2000

Angew. Chem. Int. Ed.

270

186

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Organocopper reagents provide the most general synthetic tools in organic chemistry for nucleophilic delivery of hard carbanions to electrophilic carbon centers. A number of structural and mechanistic studies have been reported and have led to a wide variety of mechanistic proposals, some of which might even be contradictory to others. With the recent advent of physical and theoretical methodologies, the accumulated knowledge on organocopper chemistry is being put together into a few major mechanistic principles. This review will summarize first the general structural features of organocopper compounds and the previous mechanistic arguments, and then describe the most recent mechanistic pictures obtained through high‐level quantum mechanical calculations for three typical organocuprate reactions, carbocupration, conjugate addition, and SN2 alkylation. The unified view on the nucleophilic reactivities of metal organocuprate clusters thus obtained has indicated that organocuprate chemistry represents an intricate example of molecular recognition and supramolecular chemistry, which chemists have long exploited without knowing it. Reasoning about the uniqueness of the copper atom among neighboring metal elements in the periodic table will be presented.

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Section: Organocopper Chemistrymentioning

confidence: 99%

Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry

Nakamura

Mori

2000

Angew. Chem. Int. Ed.

270

186

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“…53 Hence, we conclude that the energy densities of N 5 + N 5 -and N 2 H 4 differ (48) The energy of the N7 + N3 channel is 324 kcal/mol above 5N2 molecules using the G3 heat of formation of N7, and thus N7 + N3 is 27 kcal/mol above the N5 + N5 -ion pair. 49 The barrier 6 to form N7 + N3 from N5 + /N5 -is very similar to the endothermicity of the reaction, and this process again involves two open shell molecules. A closed shell asymptote of geometry similar to that of the end-on addition of N5 + to N5 -is N8 + N2, which is 230 kcal/mol above 5N2 at the CCSD(T)/6-311G*//MP2/6-31G* level 50 and, thus, substantially downhill from the ion pair by ∼67 kcal/mol.…”

mentioning

confidence: 88%

“…A closed shell asymptote of geometry similar to that of the end-on addition of N5 + to N5 -is N8 + N2, which is 230 kcal/mol above 5N2 at the CCSD(T)/6-311G*//MP2/6-31G* level 50 and, thus, substantially downhill from the ion pair by ∼67 kcal/mol. The N8 molecule that is formed, azidopentazole, has a barrier to formation of 4 N2 of only 13-14 kcal/mol at the CCSD(T)/6-311G* level 49 …”

mentioning

confidence: 99%

History of the AFRL/USC DARPA Program on Polynitrogen Chemistry. Volume 2

Vij¹

2004

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Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden to Department of Defense, Washington Headquarters Services, Directorate for Information Operations and Reports (0704-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. REPORT DATE (DD-MM-YYYY) 08-03-2004 REPORT TYPEFinal Technical Report, Vol. 2 (From -To) DATES COVERED SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR'S ACRONYM(S)Air Force Research Laboratory (AFMC) XC AFRL/PRSP SPONSOR/MONITOR'S REPORT10 E. Saturn Blvd. NUMBER(S)Edwards AFB CA 93524-7680 AFRL-PR-ED-TR-2004-0041, Vol. 2 DISTRIBUTION / AVAILABILITY STATEMENTApproved for public release; distribution unlimited. SUPPLEMENTARY NOTESThis report is Volume 2 of 2 volumes. Vol 1 is entitled, "The Solid Gas Singlet Delta Oxygen Generator." ABSTRACTIn the course of the High Energy Density Matter (HEDM) Program, which was initiated in 1986 by the Air Force, the potential of polynitrogen compounds for HEDM was recognized by numerous theoretical studies. However, no systematic efforts were undertaken to synthesize any of the potential candidates predicted by the theoreticians. This changed in 1998, when Dr. Oestmark from the Swedish Defense Research Agency proposed to DARPA an experimental study to prepare tetrahedral N 4 . In response to this proposal and upon urging from the Air Force Research Laboratory, DARPA issued a broad solicitation for experimental efforts and funded eight programs in the polynitrogen area. One of these programs was the effort at the Air Force Research Laboratory at Edwards Air Force Base. This effort was led by Karl Christe, who is also a Research Professor at the Loker Research Institute of the University of Southern California in Los Angeles, CA, and was expanded one year later to include a program at USC. Because of the overlap and close cooperation between these two programs, the results are summarized in a single report. SUBJECT TERMShigh energy density matter; HEDM; polynitrogen; chemistry; tetrahedral N4 NOTICEWhen U.S. Government drawings, specifications, or other data are used for any purpose other than a definitely related Government procurement operation, the fact that the Government may have formulated, furnished, or in any way supplied the said drawings, specifications, or other data, is not to be regarded by implication or otherwise, or in any way licensi...

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“…Nuclear magnetic resonance181920 and electrospray ionization–mass spectrometry2122 served as powerful tools and have been widely used in determining the structures of organocuprates in solution. The linear bonding geometry of the C–Cu–C moiety in cuprates such as MeCu(CN)Li, Me 2 CuLi and Me 2 -CuLi 3 Li X ( X =I, CN) has been well established.…”

mentioning

confidence: 99%

“…However, the role of cyanide and the difference between cyanide and other halide atoms still remain in debate9. Lipshutz et al 21. and Koszinowski and colleagues34 have pointed out the Li X could have a positive effect on the solubility of Cu X ( X =I, Br, Cl, CN) independently.…”

mentioning

confidence: 99%

Unravelling the hidden link of lithium halides and application in the synthesis of organocuprates

et al. 2017

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As a versatile metal, copper has demonstrated a wide application in acting as both organometallic reagent and catalyst. Organocuprates are among the most used organometallic reagents in the formation of new carbon–carbon bonds in organic synthesis. Therefore, revealing the real structures of organocuprates in solution is crucial to provide insights into the reactivity of organocuprates. Here we provide several important insights into organocuprate chemistry. The main finding contains the following aspects. The Cu(0) particles were detected via the reduction of CuX by nBuLi or PhLi. The Cu(II) precursors CuX2 (X=Cl, Br) could be used for the preparation of Gilman reagents. In addition, we provide direct evidence for the role and effect of LiX in organocuprate synthesis. Moreover, the EXAFS spectrum provides direct evidence for the exact structure of Li+ CuX2− ate complex in solution. This work not only sheds important light on the role of LiX in the formation of organocuprates but also reports two new routes for organocuprate synthesis.

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Analyses of Anionic Cu(I) Complexes via Electrospray Mass Spectrometry

Cited by 36 publications

References 32 publications

Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry

Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry

History of the AFRL/USC DARPA Program on Polynitrogen Chemistry. Volume 2

Unravelling the hidden link of lithium halides and application in the synthesis of organocuprates

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