The rotating cryostat technique has been modified to allow the use of laser ablation and magnetron metal evaporation sources to complement our previous studies of ground-state metal-atom and metal-cluster reactions using resistively heated sources. Pulses of neutralized metal plumes ablated from a copper disc by absorption of photons from an Nd/YAG 532 nm laser (8 ms pulse duration and 10 Hz repetition rate) were directed onto the constantly renewed surface of the solids previously deposited onto the rotating drum. The continuous beam of high-energy species formed by argon ion bombardment of a copper disc in a magnetron (operating at 300 V potential) was similarly deposited onto the solids at 77 K.Bombardment of benzene by copper from either laser ablation, [Cu(LA)], or magnetron sputtering sources, [Cu(MS)], gave composite EPR spectra at 220 K consisting of transitions from a copper–benzene complex (minor), cyclohexadienyl radicals, C6H7(B), and a strong isotropic sextet with g= 2.002 and aH(5)= 3.4 G (A). Assignments were confirmed by using C6D6 and C6H5D. For resistively evaporated copper atoms, Cu(TS), and those from electron beam heating, Cu(EB), only the Cu–benzene complex was formed. Species A is not the expected phenyl radical; this new species has hyperfine interactions which suggest a π-type radical bonded to an unobserved copper moiety. The two possible radicals, C6H5˙ and C5H5˙, are discussed in terms of structure and reaction pathways. The occurrence of such reactions only for Cu(LA) and Cu(MS) and not for Cu(TS) probably indicates that the atoms from the former sources have high kinetic energy ( > 83 kJ mol–1) and may also be electronically excited.Similar metal-mediated hydrogen transfers are observed for Cu(LA) and Cu(MS) atoms reacting with cyclohexa-1,3-diene.

Mechanism of thermal decomposition of n-butyl(tri-n-butylphosphine) copper(I)

EPR studies of the reactions of high-energy copper species with hydrocarbons using a rotating cryostat

[544-92-3] CCuN (MW 89.57)

InChI = 1S/CN.Cu/c1-2;

InChIKey = DULSAGLWMRMKCQ-UHFFFAOYSA-N


(·NaCN) [13715-19-0] C2CuN2Na (MW 138.58)

InChI = 1S/2CN.Cu.Na/c2*1-2;

InChIKey = NGRSIWGPWLJMKS-UHFFFAOYSA-N


(·LiCl) [59219-07-7] CClCuLiN (MW 131.96)

InChI = 1S/CN.ClH.Cu.Li/c1-2;;;/h;1H;;/q;;;+1/p-1

InChIKey = HTYULWBPSSSTKF-UHFFFAOYSA-M


(·2LiCl) [121340-53-2] CCl2CuLi2N (MW 174.35)

InChI = 1S/CN.2ClH.Cu.2Li/c1-2;;;;;/h;2*1H;;;/q;;;;2*+1/p-2

InChIKey = QGXKBLXNBYNHBV-UHFFFAOYSA-L


(·2LiBr) [129126-28-9] CBr2CuLi2N (MW 263.25)

InChI = 1S/CN.2BrH.Cu.2Li/c1-2;;;;;/h;2*1H;;;/q;;;;2*+1/p-2

InChIKey = CJIBYPVCFACANM-UHFFFAOYSA-L







(useful precursor for organocopper(I) and organocuprate(I) reagents1)



Alternate Name: cuprous cyanide.



Physical Data: mp 474 °C; d 2.920 g cm−3.



Solubility: insol H2O and most organic solvents. The lithium halide complexes are sol THF.



Form Supplied in: off-white solid.



Handling, Storage, and Precautions: highly toxic; must be handled with care.

Copper(I) Cyanide

The first successful synthesis and isolation of a boronic acid was reported in 1860 by Frankland in the pursuit of novel organometallic compounds. For more than a century, further studies of boronic acids were sparsely published. Suzuki and Miyaura jumpstarted the field in 1979 with an innovative carbon-carbon bond forming reaction employing an organoboronic acid and a carbon halide under palladium catalysis. Indeed, the Nobel Prize in Chemistry was awarded to Professor Akira Suzuki, along with Professors Richard Heck and Ei-ichi Negishi, in 2010 for their important contributions in palladium-catalyzed cross-coupling chemistry. Over the last 30 years, reports on organoboron compounds have increased exponentially. This dissertation describes the author’s contributions to the development of preparative methods for organoboronic acid derivatives using transition metal-catalyzed reactions of diboron reagents. A unique “mixed” diboron reagent was developed (PDIPA diboron) that contains sp 2 and sp 3 -hybridized boron atoms, unambiguously confirmed by X-ray crystallography. PDIPA diboron is sufficiently activated internally through a dative-bonding amine to selectively transfer the sp 2 -hybridized boron regioselectively, in the presence of copper, to electron deficient alkenes including α,β-unsaturated ketones, esters, amides, aldehydes, and nitriles to provide the corresponding boratohomoenolates. A unique β,β-diboration of an α,β-acetylenic ketone was also discovered.

Mechanism of thermal decomposition of n-butyl(tri-n-butylphosphine) copper(I)

Citations

EPR studies of the reactions of high-energy copper species with hydrocarbons using a rotating cryostat

Copper(I) Cyanide

Activation of diboron reagents: The development of mild conditions for the synthesis of unique organoboron compounds

VI. Organocopper Chemistry

Synthetic Procedures Involving Organocopper Reagents

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Reaction of lithium dialkyl- and diarylcuprates with organic halides

Mechanism of thermal decomposition of dibutylbis(triphenylphosphine)platinum(II)