Paul T. Wood

Organo-phosphorus–selenium heterocycles

Reaction of selenium with (PhP)5, or Li2Se with PhPCl2, gives a reactive intermediate (1) which undergoes reaction with acetone or CS2 to give new organo-phosphorus–selenium heterocycles which have been characterised by X-ray crystallography.

The coordination chemistry of silylsulphurdiimides

Abstract Reaction of RNSNSiMe 3 (R = Me 3 Si, t Bu, p -O 2 NC 6 H 4 S-) with PtCl 2 (dppe) gives, in the case of R = p -O 2 NC 6 H 4 S-, [Pt(NSNSC 6 H 4 NO 2 ) 2 (dppe)]. Reaction of (Me 3 Si) 2 N 2 S ( 1 ) or Bu t NSNSiMe 3 ( 4 ) with Pt(C 2 H 4 )(PPh 3 ) 2 gives Pt(NSNR) 2 (PPh 3 ) 2 (R = Me 3 Si or t Bu). The X-ray structure of p -O 2 NC 6 H 4 SNSNSiMe 3 reveals an essentially coplanar arrangement of the aryl and SNSN fragments. The bond lengths in the S 2 N 2 chain are more closely related to those in S 2 N 2 2− ligands than those in S 2 N 2 H − ligands. The X-ray crystal structure of [Pt(NSNSC 6 H 4 NO 2 )(dppe)] ( 5 ) confirms the expected cis square-planar coordination of the platinum by the chelate phosphine and two p -O 2 NC 6 H 4 SNSN − ligands. Of the atoms in the Sue5f8N ligand only the terminal nitrogen atoms lie in the platinum coordination plane. The rest of these ligands are essentially planar with their backbones trans- axial and approximately normal with respect to the PtN 2 P 2 plane.

Phosphorus–selenium heterocycles

The synthesis of the first examples of four and five membered phosphorus–selenium ring compounds PhP(Se)Se2P(Se)Ph (a selenium analogue of Lawessons reagent) and (PhP)3Se2via a number of routes is described, the new compounds being characterised by mass spectrometry, 31P, and 77Se n.m.r.

Oxidative addition reaction between lawesson's reagent and Pt(C2H4)(PPh3)2: The preparation and X-ray structure of [Pt{(S2P(S)(C6H4OMe)}(PPh3)2]

Abstract Reaction of Lawessons reagent (1) with Pt(C2H4)(PPh3)2 in benzene gives cis-Pt{S2P(S)(C6H4OMe)}(PPh3)2 (2), in 63% yield. (2) was characterised by IR, 31P NMR and X-ray crystallography: monoclinic, space group P21/c with a = 10.489(3), b = 18.373(7) and c = 22.591(9) A, β = 91.34(3)°. The molecule has square planar platinum co-ordination with non-equivalent Ptue5f8S bond lengths [2.369(2), 2.351(2) A] and a folded (19.4° dihedral angle) PtS2P ring. The Pue5f8S bond lengths are equal.

The preparation of M(PR3)2 (S2(S)PC6H4OMe) (M=Ni, Pd, Pt) from Lawessons reagent

SummaryReaction of Lawessons reagent (MeOC6H4P(S)S2P(S)C6H4OMe) (1) withbis-phosphine-dihalide complexes of nickel, palladium and platinum proceeds with asymmetric bridge cleavage to give M(PR3)2(S2(S)PC6H4OMe) (2). The new compounds were characterised by31P n.m.r., i.r. and microanalyses.

New Phosphorus-Selenium Heterdcycles

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.

Cyclic and cage ligands of elements of groups 15 and 16

Discussion de la reactivite des sulfures de phosphore simples (P 4 S 3 ) et des composes cage apparentes, avec les metaux de transition

The preparation and X-ray structure of naphthalenedithiadiphosphetanedisulphide

Reaction of P4S10 with α-bromonaphthalene at 240 °C gave the title compound, (1), in 25% yield, the first example of a six-membered (C3P2S) organo-P–S ring, the X-ray structure of which reveals a novel folded P2S2 ring.

Solid-state phosphorus-31 nuclear magnetic resonance spectroscopy of phosphorus sulphides

Magic-angle spinning 31P n.m.r. spectra of solid binary phosphorus sulphides P4Sn(n= 3, 5,7, 9, or 10) have been obtained. The multiplicity of 31P resonances are correlated with the structural inequivalences revealed by X-ray diffraction. In the case of P4S5there are considerable solution-to-solid changes in the chemical shifts. Spinning side band analysis of the solid-state spectra has yielded data on effective shielding tensor components.

Synthesis of M2Ag6S4(M = Na, K) in supercritical ethylenediamine solvent: a novel solid containing unusual closed-shell bonding

A novel solid M2Ag6S4(M = Na, K) has been synthesized in supercritical ethylenediamine, and has an unusual framework structure with an extended array of face-sharing silver octahedra