Bonds to Sulphur or Selenium

Watanabe, S. Sato, and H. Saito, Bull. Chem. Soc. Japan, 1975, 48, 896. 

Tranquard, Bull. Soc. chim. France, 1975, 1484. 

S-Se compounds were identified in a number of systems investigated, including P4Se3-P4S3, P4 e4-P4S7, P4Seio-P4Sio, and P4S,o-Se.  

A value of 0.91 D has been calculated for the free electron-pair moment in P compounds, using dipole-moment data for P4S3 and the phosphabicyclo-octane derivative (110). Calculations for the compounds in the series PH Me3 with n - 0—3 point to variation in the free electron-pair moment as being the most important factor in determining the observed dipole moments extension to a variety of other species allows the calculation of new values for the moments of typical bonds to phosphorus. 

Bonds to Sulphur or Selenium.— Values for the dissociation energies (Do) of the diatomic species PS, PSe, and PTe, determined by Knudsen-cell mass spectrometry, are 438, 360, and 294 kJ mol 1, respectively.583 Some 3lP n.m.r. data for P4S3 in the polycrystalline state584 and in a nematic phase are now available.585 Displacement of one carbon monoxide group from Mo(CO)6 occurs on reaction with P4S3, giving (84),586 and crystal data show 

Carbon disulphide inserts rapidly into the P—N bond of N-dimethyl-aminophosphines containing phosphorus-sulphur bonds to give thiocarba-moyl derivatives such as Me2NC(S)SPR R2, but similar reactions with 

Ghorbel, F. d Yvoire, and C. Doremieux-Morin, Bull. Soc. chim. France, 1974, 1239. 

Preparative methods have been devised for two new phosphonothioic dichlorides RP(S)C12, where R = 2-chlorocyclohexyl and 1-cyclohexen-l-yl,594 and for the pentafluorophenyl derivatives C6F5P(S)X2, R(C6F5)P(S)X, and (C6Fs)2P(S)X.595 Compounds with the general formula [R2P(X)]2Y, where X and Y = O or S, have been prepared for detailed n.m.r. 

Ph2P(S)SP(S)Ph2 + (Me2N)2S — Ph2P(S)SSNMe2 + Ph2P(S)NMe2 (20) (86) 

Bonds to Sulphur or Selenium.—Structures (114) and (115), respectively, are assigned on the basis of i.r. data, etc.y to the sulphides P4S9 and P4S4 obtained 

729 D Tranqui, M. Bagieu-Beucher and A. Durif, Bull. Soc. franp. Min rale Crist., 1972, 95,437. 

Bagieu, I. Tordjman, and G. Bassi, Cryst. Struct. Comm., 1973, 2, 387. 

Mild alkylation of (R2NCH2CH20)2P(S)SK gives the triesters, which are unstable and undergo thione-thiol isomerization. Treatment of P2S5 with alkanethiols in the presence of triethylamine produces the heterocycle (117), which can be converted into the potassium salt by potassium ethoxide,  

Bonds to Sulphur or Selenium.—Reviews have appeared on phosphorus sulphides and selenides and on the chemistry of chiral thio- and seleno-derivatives of a range of phosphorus acids.  

Ternary compounds that have been isolated and investigated during the period under review include NiPS, CoMS and CoMSe (M = P, As, or Sb), and Zni, Fe,PS3.  

Nahigian, J. Steger, and A. Wold, Inorg. Chem., 1975, 14, 2912. 

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Bonds to Sulphur or Selenium.— Arsenic, antimony, and bismuth trichlorides react with bis(2-mercaptoethyl) sulphide, liberating hydrogen chloride and forming the cyclic compounds (99).686 Complete spectroscopic data... 

Bonds to Sulphur or Selenium.—A polymeric anion (136) formed from edge-sharing pseudo-trigonal-bipyramidal units is present in the red thioantimonite... 

Bonds to Sulphur or Selenium.—Gas-phase laser Raman spectra of mixed arsenic-sulphur vapours show that the arsenic-rich mixtures contain AS4, AS4S3, AS4S4, and AS2S2. Far-i.r. and 1 and As n.q.r. spectra for AS2S3 and AsSI and the selenium analogues have been measured. ... 

Bonds to Sulphur or Selenium.— The crystal structure of Bi2ln4S9, recently synthesized by vapour-transport reactions with iodine, indicates that three of the indium atoms are octahedrally co-ordinated by sulphur while the fourth... 

Bonds to Snlphur or Selenium.—Rapid cooling of a 1 1 mixture of arsenic and sulphur from ca. 550 °C led to the isolation of a new isomeric form of AS4S4 with a structure derived from an AS4 tetrahedron, as shown in Figure 7. Mean As—S and As—As distances are 2.244 and 2.535 A, respectively, while values for the AsAsAs, AsAsS, SAsS, and AsSAs angles are 83.2, 95.8, 101.2, and 105.2 ,... 

In this section we will describe some PES investigations on Group XIV element derivatives in which one or more sulphur or selenium atoms are bonded directly or indirectly to the metal120-132. The aspects investigated preferentially for these molecules were the electronic and conformational situation, the role played in the bonding by the chalcogen lone-pair orbitals and possible hyperconjugative interaction (n-cr or p -d ). 

Figure 33 shows the UPS spectra of 2,5-bis(diphenylmethy-lene)-2,5-dihydrothiophene and di-hydroselenophene, as compared with that of 2,5-bis(dithienyl methy-lene)-2,5-dihydrothiophene, together with the spectra of benezene and thiophene for references, irrespective of the central ring with sulphur or selenium the UPS spectra are found to be almost same. However, the spectra were significantly different with changing the substituent rings at the exocyclic double bonds from the phenyl to the thienyl groups. In both the phenyl and the thienyl substituents, the spectra are very similar to those of benzene and thiophene... 

Analogous trends, although to a lesser extent, appear in selenocarboxylic acid derivatives as soon as third- and/or higher-row elements (sulphur or selenium) are involved, the 8 C Se) reach up to 5 = ca. ISOO. It seems that the interaction of the lone-pairs of these chalcogen atoms with the C=Se 7i-bond (formula II in Scheme 24) is less effective.2 These trends may be demonstrated in a series of selenoesters Ph-C(=Sc) X X = NMc2, 5 = 733 X = OMe, 5 = 910 X = SeMe, 5= 205 correlations of Se... 

The reaction products obtained when dissolving elemental selenium in aqueous sulphite solution were found to be ScSC), and some reactions using similar sulphur or selenium reagents afforded the ScfSOi) isomers with O- and with S-bonded Se as well as other related species, as determined by Se NMR and Raman spectroscopy. Selenium dioxide, ScC)2. is the... 

The mass spectra of a number of heterocyclic compounds have been reported. The fragmentation patterns of thiophosphoryl derivatives of phosphorinanes are sensitive to stereochemistry, thus for the series (95) facile loss of the HS radical is indicative of an axial PS bond. The seven-membered heterocycles (96 Ch = S, Se) undergo a remarkable migration of sulphur or selenium from phosphorus to carbon with ring cleavage. While exocyclic P-C bonds of five-and six-membered heterocycles in the phosphonic class may be readily cleaved with retention of the phosphorus ring system, the seven-membered ring (97) exhibits facile expulsion of a phosphorus radical. ... 

For the N-bonded isomers, the Hg + can easily attack the free sulphur or selenium atoms of the ligands, so the equilibrium is displaced to the right and the rate law reduces to kexD = ki since ki for the spontaneous solvolysis is approximately 3 X 10 times smaller than kf for the mercury(ii)-accelerated one. For the sulphur-or selenium-bonded isomers on the other hand, the rate law (10) reduces to A e.xp = A i X[Hg +]. It should be noted that in this case the experiments cannot... 

A further, substantial group of compounds all contain square-planar Te° atoms bonded to two pairs of sulphur or selenium ligands in a trans structure. The geometries may again be conveniently tabulated [formula (3) and Table 3]. 

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