Solvent extraction of metal xanthates

Donaldson, Elsie M.

doi:10.1016/0039-9140(76)80121-x

Cited by 47 publications

(7 citation statements)

References 29 publications

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“…While the chemistry of metal xanthates has been the subject of study for many years, driven by applications in both analytical chemistry and metal extraction (Rao, 1971;Magee, 1973;Donaldson, 1976;Rao and Ramakrishna, 2003), recent years have seen a renaissance in the area resulting from the use of metal xanthates as single-source precursors (SSPs) to metal sulphide materials (Nair et al, 2002;Koh et al, 2003;Han et al, 2007;Clark et al, 2011;Liu et al, 2011;Rath et al, 2013;Kociok-Köhn et al, 2014). Remarkably, despite reports of ca.…”

Section: Introductionmentioning

confidence: 95%

Amino-funtionalised metal xanthates

Hill

Kociok‐Köhn

Molloy

et al. 2015

Main Group Metal Chemistry

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The amino-functionalised xanthate NaS 2 COC 2 H 4 N(Me)C 2 H 4 NMe 2 (1) was synthesised, and its structure was determined to be a coordination polymer incorporating a six-coordinate metal with S 3 N 2 O ligation and in which the ligand delivers κ 2 -S,S chelate, κ 2 -S,O chelate, κ 2 -N,N chelate, and μ 2 -S bridging modes. 1 has been used to prepare the copper complex (Ph 3 P) 2 CuS 2 COC 2 H 4 N(Me) C 2 H 4 NMe 2 (5), although reactions with various Zn(II) and Cd(II) salts yielded only the metal sulphide decomposition product and the free acid as its 1,1,4-trimethylpiperazinium salt (2). Attempts to insert CS 2 into the alkoxides RMOC 2 H 4 N(Me)C 2 H 4 NMe 2 (M = Zn, R = Et [3]; M = Cd, R = Me [4]) also failed to give the desired group 12 derivative of the amino-functionalised xanthate. The structures of 2-5 are also reported.

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Section: Introductionmentioning

confidence: 95%

Amino-funtionalised metal xanthates

Hill

Kociok‐Köhn

Molloy

et al. 2015

Main Group Metal Chemistry

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“…Specifically, we reported a general method based upon the controlled in‐situ thermal decomposition of a single‐source precursor (namely a metal dithiocarbonate, also called metal xanthate) in a semiconducting polymer film 21. The use of metal xanthate based precursors is particularly attractive for this purpose due to the possibility of controlling their solubility, air‐stability (under ambient conditions) and decomposition temperature through well established synthetic procedures 21, 22. In addition, metal xanthates are known to decompose cleanly at low temperatures into the metal sulfide, generating only volatile side products (typically H 2 S, COS and ethene for the ethyl xanthate), thereby enabling the in‐situ growth of inorganic nanoparticles in relatively fragile polymer hosts.…”

Section: Current‐voltage Characteristics Of the Photovoltaic Devicesmentioning

confidence: 99%

The Rearrangement of the Cubane Radical Cation in Solution

et al. 2001

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The rearrangement of the cubane radical cation (1*+) was examined both experimentally (anodic as well as (photo)chemical oxidation of cubane 1 in acetonitrile) and computationally at coupled cluster, DFT, and MP2 [BCCD(T)/cc-pVDZ//B3LYP/6-31G* ZPVE as well as BCCD(T)/cc-pVDZ//MP2/6-31G* + ZPVE] levels of theory. The interconversion of the twelve C2v degenerate structures of 1*+ is associated with a sizable activation energy of 1.6 kcalmol(-1). The barriers for the isomerization of 1*- to the cuneane radical cation (2*+) and for the C-C bond fragmentation to the secocubane-4,7-diyl radical cation (10*+) are virtually identical (deltaH0++ = 7.8 and 7.9 kcalmol(-1), respectively). The low-barrier rearrangement of 10*+ to the more stable syn-tricyclooctadiene radical cation 3*+ favors the fragmentation pathway that terminates with the cyclooctatetraene radical cation 6*+. Experimental single-electron transfer (SET) oxidation of cubane in acetonitrile with photoexcited 1,2,4,5-tetracyanobenzene, in combination with back electron transfer to the transient radical cation, also shows that 1*+ preferentially follows a multistep rearrangement to 6*+ through 10*+ and 3*+ rather than through 2*+. This was confirmed by the oxidation of syn-tricyclooctadiene (3), which, like 1, also forms 6 in the SET oxidation/rearrangement/electron-recapture process. In contrast, cuneane (2) is oxidized exclusively to semibullvalene (9) under analogous conditions. The rearrangement of 1*+ to 6*+ via 3*+, which was recently observed spectroscopically upon ionization in a hydrocarbon glass matrix, is also favored in solution.

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“…Although the chemistry of metal xanthates, M(S 2 COR) n , has been investigated for over a century, fueled by applications in analytical chemistry and metal extraction (Rao and Singh, 1971;Magee, 1973;Donaldson, 1976;Rao and Ramakrishna, 2003), there has been something of a renaissance of activity in recent years as these species become the precursor of choice for the deposition of many metal sulfide thin films. Their ease of synthesis, general aerobic stability and, particularly, their facile decomposition via a Chugaev mechanism (Tschugaeff, 1900), thus affording low deposition temperatures, have attracted the interest of scientists as single-source precursors to a variety of sulfide-based materials (Bessergenev et al, 1998;Nair et al, 2002;Koh et al, 2003;Barreca et al, 2005;Han et al, 2007;Clark et al, 2011;Liu et al, 2011;Rath et al, 2013;Kociok-Köhn et al, 2014).…”

Section: Introductionmentioning

confidence: 99%