Ambident nucleophiles

Thispaper is dedicated to Professor Douglas E. Ryarz on the occasior~ of his 65th birthday CORRADO GELOSO, RAJESH KUMAR, JAIME ROMERO LOPEZ-GRADO, and DENNIS G. TUCK. Can. J. Chem. 65, 928 (1987).Dialkyldithiocarbamate derivatives (R,NCS~),,M of a number of metals (M = Fe, Co, Ni, Cu, Ag, Zn, Cd, In, T1) have been synthesised in good yield by electrochemical oxidation of appropriate sacrificial anodes in non-aqueous solutions of either the corresponding tetraalkylthiuram disulphide (RzNCS2)2 (R = Me, Et) or a mixture of carbon disulphide plus the secondary amine R2NH (R = Et, i-Pr; R2NH = piperidine). Similar experiments with solutions of (EtO),P(S)SH (= HL) gave ML, derivatives (M = Fe, Co, Ni, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, T1) while in the presence of HL + 1 ,lo-phenanthroline, ML,, .phen derivatives were obtained for M = V, Mn, Fe, Co, Zn, and Ga.CORRADO GELOSO, RAJESH KUMAR, JAIME ROMERO LOPEZ-GRADO et DENNIS G. TUCK. Can. J. Chem. 65, 928 (1987).On a synthCtisC avec de bons rendements les derives dialkyldithiocarbamates (R2NCS2),,M d'un certain nombre de metau (M = Fe, Co, Ni, Cu, Ag, Zn, Cd, In, T1) en mettant en jeu l'oxydation Clectrochimique d'anodes sacrifices appropriees dans des solutions non-aqueuses soit des disulfures de tCtraalkylthiurames correspondants (R2NCS2)2 (R = Me, Et) soit d'un melange de disulfure de carbone plus l'amine secondaire R2NH (R = Et, i-Pr; RzNH = piperidhe). Des experiences semblables avec des solutions de (EtO)?P(S)SH (= HL) conduisent aux derives ML,, (M = Fe, Co, Ni, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, T1) alors que, en presence de HL + phenanthroline-l,10, on obtient des derives ML,, .phen (M = V, Mn, Fe, Co, Zn et Ga).[Traduit par la revue]

Section: Diethyldithiophosphate Compourzdssupporting

confidence: 83%

The direct electrochemical synthesis of dialkyldithiocarbamate and diethyldithiophosphate complexes of main group and transition metals

Geloso¹,

Kumar²,

Lopez-Grado³

et al. 1987

“…The 3 1~( H ) NMR spectra, which are presented in Table 9 along with the 'H NMR data, show a single peak in all compounds 1-6, consistent with both dithiophosphate groups in 4-6 being in identical environments. It has been proposed that the difference in the phosphorus chemical shift between a derivative and that of the free acid, AP, is an accurate indicator of the mode of binding (33). Thus, downfield shifts in the range AP = 8-15 ppm are associated with bidentate ligands, and negligible shifts or even upfield shifts are associated with monodentate linkages.…”

Section: Compoundmentioning

confidence: 99%

A study of a variety of O,O-alkylene dithiophosphate derivatives of triphenyl-and diphenylgermane. Crystal structures of and

Drake¹,

Mislankar²,

Ratnani³

et al. 1995

The O,O-alkylene dithiophosphate derivatives of triphenyl- and diphenylgermane, [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] and [Formula: see text] have been prepared and characterized by infrared, Raman, and 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and, in three cases, X-ray crystallography. [Formula: see text] 1, crystallizes as monoclinic in the space group P21/a (No. 14) with the cell parameters a = 12.868(5) Å, b = 11.354(4) Å, c = 17.207(4) Å, β = 95.42(2)°, V = 2502(1) Å3, Z = 4, R = 0.0640, and Rw = 0.0585. [Formula: see text] 2, crystallizes as orthorhombic in the space group Pbca (No. 61) with the cell parameters a = 23.007(4) Å, b = 16.840(4) Å, c = 12.068(3) Å, V = 4657(3) Å3, Z = 8, R = 0.0502, and Rw = 0.0329. [Formula: see text] 3, crystallizes as monoclinic in the space group C2/c (No. 15) with the cell parameters a = 35.48(2) Å, b = 9.275(5) Å, c = 20.78(1) Å, β = 120.93(3)° V = 5866(5) Å3, Z = 8, R = 0.0674, and Rw = 0.0562. As with their methylgermanium analogues, the environment about germanium is essentially that of a distorted tetrahedron, with the terminal sulfur atoms oriented towards germanium rather than away from it, in contrast with analogous noncyclic dithiophosphatogermanes. The substituents on the atoms in both the five- and six-membered rings maintain their nonequivalence in solution, in contrast with tin analogues. Keywords: structure, germanium, diphenyl, triphenyl, cyclic dithiophosphates

“…This indicates the presence of only one species and also that the two dithiophosphate groups are in identical environments. It has been proposed that the difference in the phosphorus chemical shift between that of the appropriate free acid and the derivative is a strong indicator of the mode of binding (47). Downfield shifts in the.…”

Section: Nuclear Magnetic Resonance Spectramentioning

confidence: 99%

Synthesis, spectroscopic, and structural studies of dimethyltellurium(IV) alkylene and diphenyl dithiophosphates. Crystal structures of and

Drake¹,

Khasrou²,

Mislankar³

et al. 1994

and -CH2CEt2CH2-, have been synthesized in 80-90% yields by reaction of the corresponding sodium or ammonium salts of the appropriate dithiophosphoric acids with dimethyltellurium dichloride in toluene. Me,Te[S,P(OPh),], was also prepared in a similar fashion. The compounds have been characterised by elemental analyses -and 'H, l3C, 3 '~, and ' 2 5~e NMR, infrared and Raman spectroscopy. = 0.0295. The immediate environment about tellurium in both molecules is that of the saw-horse structure typical of tellurium(1V) compounds with the two methyl groups equatorial and one sulfur atom from each dithiophosphate group occupying the axial positions. The consideration of the second sulfur atom as part of the coordinating sphere is discussed in terms of a modification of Pauling's approach to partial bond orders. The 'H NMR spectra suggest that these dithiophosphates may be fluxional in solution andlor that there is rapid exchange of the sulfur atoms.