Synthesis and Structure of Surprisingly Stable Tetrakis(trifluoromethyl)cuprate(III) Salts

Abstract

=1.56 gcm-'; max. 2 0 = 4 4 (Mo,,, i = 0.70930 A. graphite monochromator, w/20-Scan, 7'= 223 K); 4447 reflections measured. 4180 independent, 3950 observed [Fo 3 u(Eo)], Lorentzian polarization and empirical absorption corrections ( p = 21.4 cm-l, $-scan method, min. transmission 84.1 I O h ) ; direct methods (SHELXSX6). refinement with program package SDP (Enrdf-Nonius), positions of hydrogen atoms calculated according to ideal geometry (C-H distance 0.95 A): R = 0.0285, R, = 0.0395; reflexiparameter ratio 12.5, residual electron density +0.582/-0.910 e k 3 . Further details of the X-ray structure analysis are available on request from the FachinformationsLentriim Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH. D-76344 Eggenstein-Leopoldshafen (FRG), on quoting the depository number CSD-57 130, the names of the authors. and the journal citation.

The Trifluoromethyl Group in Transition Metal Chemistry

“…For instance, the mixed oxidation state compound Ag I [Ag III (CF 3 ) 4 ] was obtained in 80-86 % yield by reaction of AgNO 3 with Cd-(CF 3 ) 2 ·2MeCN in MeCN solution. This geometry is typical in four-coordinate d 8 metal complexes and is therefore in keeping with the Cu III oxidation state originally assigned to the metal center; [152] this assignment has been somewhat debated. The cuprate salt [CdI] + [Cu III (CF 3 ) 4 ]was first obtained in 1989 by oxidation of [CdI] + [Cu I (CF 3 ) 2 ]with oxygen, iodine, or bromine although no details on the synthetic procedure were given.…”

“…This is clearly illustrated in the isoleptic series of anionic species [M III (CF 3 ) 4 ]for the Group 11 metals including the lighter ones (M = Cu, [62,152] Ag, [91] Au). This is clearly illustrated in the isoleptic series of anionic species [M III (CF 3 ) 4 ]for the Group 11 metals including the lighter ones (M = Cu, [62,152] Ag, [91] Au).…”

“…The synthetic methods used to prepare them cannot be considered merely as oxidative additions as they also involve ligand-exchange processes. [152] The molecular structure of the [N(PPh 3 ) 2 ]-[Cu(CF 3 ) 4 ] salt revealed a nearly square-planar arrangement of the CF 3 groups around the metal center (Figure 16). [91] In this system, the organocadmium(II) compound clearly acts as a CF 3 -group transfer reagent, while the nature of the oxidizing species remains unclear.…”

Highly Trifluoromethylated Platinum Compounds

“…À anions for all three Group 11 metals (M III = Cu, [15] Ag, [16] Au [17] ) has also been prepared. [18] We have recently reported [12] 2À has also been detected as a solution species by other authors.…”

Quantum chemistry of organocuprates as intermediates of catalytic and photochemical reactions

“…[3] Some experimental evidences of formation of adducts between copper complexes and organic radicals were obtained, [4][5][6][7][8][9][10][11][12][13][14] but the information on their structure was very scarce. Over the last years organometallic chemistry of Cu(I) and Cu(III) was vastly in progress [15,16] in contrast to Cu(II); only few stable organocuprates (II) are known to date. [17][18][19][20][21][22][23][24] Meanwhile, due to spectral data not a few labile transients, probably compounds with Cu(II)AC bond, may form in conditions of catalytic and photochemical reactions or directly by reaction of Cu(I) complexes with organic radicals.…”