"Phosphorus, Sulfur, and Silicon and the Related Elements"

Holmes, Robert R.

doi: 10.1080/10426508908039684pmid: N/A

doi: 10.1080/10426508908039683pmid: N/A

Abstract This is a scanned image of the original Editorial Board page(s) for this issue.

West, Robert; Gillette, Gregory R.; Yokelson, H. B.; Millevolte, A. J.

doi: 10.1080/10426508908039685pmid: N/A

Abstract Disilenes, R2Si=SiR2, react with many substances to produce cyclic compounds containing two silicon atoms and one or more heteroatoms. Host of these products are new ring systems, and some show abnormal structures with short Si-Si bonds, suggesting unusual chemical bonding.

Wells, Richard L.; Holley, William K.; Shafieezad, Soheila; McPhail, Andrew T.; Pitt, Colin G.

doi: 10.1080/10426508908039686pmid: N/A

Abstract (1) has been isolated from the products of the room temperature reaction of Ph2GaCl with (Me3Si)3As (reactants mixed in both a 2:1 and a 3:1 mole ratio). A mixture of 1 and [Ph2GaAs (SiMe3)2]2 (2) was isolated after heating a 1:1 mole ratio combination of the same reactants. Reaction of pure 2 [prepared from Ph2GaCl and LiAs(SiMe3)2] with Ph2GaCl resulted in the formation of (1). Prolonged heating of 1 produced a mixture of 2, Me3SiCl and unidentified products. Compound 1 was structurally characterized by a single-crystal X-ray analysis and shown to be the first organogallium four-membered ring compound with both an arsenic and a halogen bridge. The ring of 1 is clearly non-planar as evidenced by the fact that the Cl atom is displaced from the Ga-As-Ga' plane to yield a dihedral angle of 8.8° between the Ga-As-Ga' and Ga-Cl-Ga' planes. Various other features of the structure of 1 are discussed.

Gudat, D.; Lensink, C.; Schmidt, H.; Xi, S.-K.; Verkade, J. G.

doi: 10.1080/10426508908039687pmid: N/A

Abstract The synthesis of the new pro-phosphatranes YP(MeNCH2CH2)3N (Y = lone pair, 0, S, Se, BH3 and CH3 +) containing four-coordinate phosphorus, and the tbp phosphatranes are reported. New azasilatranes of the type are also reported and the results of nucleophilic substitution studies of the labile hydrogen on the equatorial nitrogens are given.

Sita, Lawrence R.; Bickerstaff, Richard D.

doi: 10.1080/10426508908039688pmid: N/A

Abstract The stannylenes, R2Sn: [R = bis(trimethylsily1)-methyl and 2,4,6-triisopropylphenyl], react with 3,3,6,6-tetramethyl-1-thia-4-cycloheptyne to give the corresponding stannacyclopropenes. Full characterization of these derivatives, including crystallographic analysis, reveals some insight into the nature of bonding in stannacyclopropenes.

Burford, Neil; Royan, Bruce W.

doi: 10.1080/10426508908039689pmid: N/A

Abstract As a contribution to the development of general stable pπ-pπ bonding throughout the p-block, the first dithiaphosphenium cation la has been prepared. Stable dicoordinate phosphorus without the presence of at least one nitrogen or carbon ligand is unique. Moreover, this compound contains an unprecedented example of thermodynamically stable pπ-pπ bonding between phosphorus and sulfur. In addition, cation la contains a rare example of pπ-pπ bonding between the heavier elements of different groups of the Periodic Table. The analogous arsenic and antimony derivatives have been prepared, demonstrating that the system offers potential generality for genuine pπ-pπ bonding between all heavy (n > 2) non-metal elements.

Cavell, Ronald G.; Katti, Kattesh V.

doi: 10.1080/10426508908039690pmid: N/A

Abstract The first examples of phosphiniminatophosphanes, Me3SiN=P(Ph2)(CH2)nP(Ph2), were prepared from the reactions of the diphosphanes, Ph2P(CH2)nPPh2 [n = 1 and 2], with N3SiMe3. ARPHOS, Ph2As(CH2)2PPh2, is oxidized only at phosphorus to yield a new phosphiniminatoarsane. These new heterodifunctional ligands with both hard and soft centres react with metal compounds to yield chelates and metal-nitrogen bonded metallacycles. The Rh(l) carbonyl derivatives of these ligands convert methanol to acetic acid in the presence of CO and CH3l. Re(VII) reacts with Ph2PCH2(Ph2)P=NSiMe3 to form a Re-N metallacycle. Alkyl and aryl germanium halides suffered germanotropic rearrangements and loss of organic subsituents in reaction with the doubly oxidized diphosphane, Me3SiN=P(Ph2)CH2(Ph2)P=NSiMe3, to form a new germanium spirocycle containing both Ge-C and Ge-N bonds. The isomeric spirocycle with only Ge-N bonds was also prepared from GeCl4 and the bis(phosphiniminato)methane and from a germanium diazide and dppm. Structural confirmation of all of the new metallacyclic compounds was provided by complete 1H, 13C, 31P and 29Si NMR studies.

Wood, Paul T.; Woollins, J. Derek

doi: 10.1080/10426508908039691pmid: N/A

Abstract The preparation of new phosphorus-sulphur and phosphorus-selenim heterocycles is described. The new compounds have been characterised by multinuclear NMR (31P, 77se) and x-ray crystallography.

Hahn, Josef; Borkowsky, Anno; Nataniel, Tina

doi: 10.1080/10426508908039692pmid: N/A

Abstract Sulfur phosphorus heterocycles of general composition RP(S)Sn and [RP(S)Sm]2 have been synthesized from silyl and stannyl esters of trithiophosphonic acids RP(S)(SEMe3)2 (E = Si, Sn). The phosphorus-31 nucleus has been used as an NMR probe for the study of ring reversal and related dynamic processes. The results obtained, provide insight into the mechanism and energy barrier of the crown reversal of cyclo-octasulfur. Moreover, some of the hetero-cycles show configurational changes at the P atoms as well as reversible oligomerization reactions.