Synthesis,crystal structure,and NMR spectroscopy of a 1,3,2λ5,4λ5-oxathiadiphosphetane

From the crude product of the synthesis of the dithiadiphosphetane [RP(S)S]₂ (with R = 2,4,6-iPr₃C₆H₂), the trans-oxathiadiphosphetane has been isolated, C₃₀H₄₀OP₂S₃. X-ray structure analysis and mass spectroscopic investigations give unequivocal evidence for this structure: monoclinic, C2/c (no. 15), a = 13.066(8), b = 21.726(8), c = 12.070(6) Å, β = 103.54(10)°, V = 3331 ų, Z = 4, and D_c = 1.158 g/cm³. The asymmetric unit consists of half the formula unit. Solid-state ³¹P NMR spectra give information about the chemical shift anisotropy. Results of IGLO calculations of the ³¹P nuclear magnetic shielding tensor agree satisfactorily with the experimental data. Monitoring the reaction of several dithiadiphosphetanes with benzophenone in solution by ³¹P NMR spectroscopy indicates that additional oxathiadiphosphetanes as well as thiotrimetaphosphonates are present. © 1996 John Wiley & Sons, Inc.     

Reactions of dithioxo-1,3,2λ5,4λ5-dithiadiphosphetanes with triorganolead derivatives

The reactions of Lawesson's reagent 1a and its 4-ethoxy homologue 1b with triethyl- and triphenyl(alkoxy)plumbanes 2a,b and -(alkylthio)plumbanes 4a,b were studied. On the basis of these reactions, novel, advantageous methods of synthesizing S-triethyl and triphenylplumbyl derivatives of aryldithio- and trithiophosphonic acids 3a–d and 5a,b were developed. © 1997 John Wiley & Sons, Inc.     

Reactions of dithioxo-1,3,2λ5,4λ5-dithiadiphosphetanes with trialkylsilyl and stannyl derivatives

The reactions of homologues of Davy's reagent 1 and Lawesson's reagent 9 with trimethylalkylthiosilanes 2 , trimethylsilyl enol ether 4 , trimethyl(diethylamino)silane 7 , trialkylalkoxystannanes 14 , and trialkylalkylthiostannane 15 were studied. On the basis of these studies, novel advantageous methods of synthesizing S-trialkylsilyl and stannyl esters of tetrathio-, trithio-, and amidotrithiophosphoric acids 3 , 5 , 6 , and 4-methoxyphenyldithio- and trithiophosphonic acids 10–13 were developed     

Reactions of dithioxo‐1,3,2λ5,4λ5‐dithiadiphosphetanes with antimony(III) alkoxides

New antimony(III) derivatives of dithiophosphonic and trithiophosphoric acids 3a–c and 5 were obtained by the reactions of Lawesson's reagent 1a, its homologue 1b, and the isobutyl homologue of Davy's reagent 4 with antimony(III) alkoxides 2a–c. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 399–403, 1999     

1,4-Dihydro-1λ5,4λ5-[1,4]diphosphinine und ein 1,4-Dihydro-1λ3,4λ3-[1,4]diphosphinin

1,4-Dihydro-1λ⁵,4λ⁵-[1,4]diphosphinines and a 1,4-Dihydro-1λ³,4λ³-[1,4]diphosphinine Reaction of thio- or dithiocarbonic acids with ethinyl amino phosphanes leads to 1,4-dihydro-1λ⁵,4λ⁵-[1,4]diphosphinine-1,4-disulfides. By this route compounds 4, 7 , and 8 have been prepared. Desulfurization of 4 with tri-n-butylphosphane results in 1,2,4,5-tetraphenyl-1,4-dihydro-1λ³,4λ³-[1,4]-diphosphinine 5 , which can be oxidized with tert-butyl-peroxide to the corresponding dioxide, 6 . From the reaction mixture of phenyl-phenylethinyl diethylamino phosphane and thioacetamide compound 4 and the unsymmetrical 1,4-dihydro-1λ⁵,4λ⁵-[1,4]diphosphinine 9 were isolated. Properties, nmr, ir and mass spectra of all new products are reported. A mechanism for the formation of 9 is suggested. The results of the X-ray structure determination of 8 and 9 are described.     

Synthesis of dimeric 1,3,2λ5-benzoxazaphospholes from phosphinic acid derivatives by silylation/desiloxylation

The reaction of N,N,O-tris(trimethylsilyl)-o-aminophenol with two equivalents of phosphinic chloride yielded dimeric 2,2-disubstituted 1,3,2λ⁵-benzoxazaphospholes and trimethylsilyl phosphinate. The chlorides having the bulk substituents (o-chlorophenyl or tert-butyl) at phosphorus or containing P N and P O bonds (instead of a P C bond) either didn't react at all or reacted to retain the phosphoryl group. Being stable in solution at 20°C, the individual diastereoisomers of dimeric 1,3,2-benzoxazaphospholes were converted upon warming to an equilibrium mixture of isomers. When reacted with another dimer each gave a mixed dimeric compound having two different phosphorus atoms in the molecule.