In recent years, research in organophosphorus chemistry has mainly focused in designing newer and better phosphorus ligands for synthesizing novel metal complexes with improved catalytic activities. Aminophosphines [tricoordinate phosphorus(III)–nitrogen systems] are considered as versatile compounds owing to the presence of nitrogen centres which, in principle, can influence additional reactivity features. They are quite sensitive to air and moisture due to the presence of polar PN bond(s). In spite of this, research in aminophosphine chemistry is gaining momentum day-by-day and this is due mainly to one reason: their rich behaviour as ligands in metal complex chemistry and subsequently in catalysis. Their role as synthons in inorganic heterocyclic chemistry has also helped produce new types of heterocycles. In this paper, the chemistry of simple acyclic aminophosphines (synthesis, characterization, reactivity and applications) is covered and particular focus is given to their ability to form chalcogenides along with their role played as ligands in coordination chemistry and as synthons in inorganic heterocyclic chemistry. Copyright © 2009 John Wiley & Sons, Ltd.

Aminophosphines: their chemistry and role as ligands and synthons

An electron rich “hybrid” asymmetric aminophosphine, (diisopropylamino)(morpholino) (phenyl)phosphine, L, was synthesized in good yield by step‐wise aminolysis reactions with dichloro(phenyl)phosphine and structurally characterized. The complex, CuCl(L) was readily isolated from both 1∶1 and 1∶2 reactions of L with CuCl. Single crystal X‐ray structures of L and two copper complexes, [CuCl(L) · CH3CN]2 (1) and [CuCl(L) · CH2Cl2]2 (2) have been determined. X‐ray structures reveal pyramidal nature of phosphorus and near planar geometry of nitrogen of the phosphine ligand and the dimeric nature of the complexes with tricoordinate copper(I) centers. The asymmetric phosphine crystallizes in monoclinic system with space group P21/c and unit cell dimensions as a=17.219(1) A, b=13.469(1) A, c=7.395(5) A, α=90.00°, β=93.11(1)°, γ=90.00°. Both acetonitrile (1) and dichloromethane (2) solvates crystallize in triclinic system with space group Pī. The unit cell dimensions of (1) are a=10.143(2) A, b=13.681(3) A, c=16.6...

Synthesis and X‐ray Structural Characterization of (Diisopropylamino)(Morpholino)(Phenyl)Phosphine and its Dimeric Copper(I)

The title compound (NC4H8NCH3)(C6H5)[N(C6H11)2]P{—N–S3N3 crystallizes in the triclinic crystal system with unit cell dimensions: a = 9.7572(2), b = 10.6845(1), c = 16.9381(3) A, α = 71.75(1)∘, β = 80.65(2)∘, γ = 65.93(1)∘, and Z = 2. The tricoordinated sulfur atom (S1) in the cyclotrithiazene deviates from the mean plane of the other five atoms by 0.716(6) A, which is the highest among the known phosphiniminocyclotrithiazene structures. In the exocyclic P{—N4–S1 moiety, the two bond distances are short: 1.585(6) and 1.527(6) A; but the bond angle is large 135.3(4)∘. The S1 displacement is highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or −1.0) for the cyclic and acyclic substituents (R) in the (R)(C6H5)[N(C6H11)2]P{—N–S3N3 series. On the other hand, the S1–N4 bond distances are negatively correlated (R = −0.94) with the P{—N4–S1 bond angle in the above series.

Crystal structure analysis of (N-methyl piperazino) (phenyl) (dicyclohexylamino) phosphiniminocyclotrithiazene

The title compound (C6H5)(C4H8NO)[N(C6H11)2]P=N-S3N3 crystallizes in a triclinic crystal system with unit cell parameters a = 9.8884(4) A, b = 10.6075(1) A, c = 14.2276(2) A, α = 78.14(3)°, β = 79.31(1)°, λ = 65.42(2)°, V = 1319.44(6) A3, Z = 2, and space group \(P\bar 1\). The cyclotrithiazene ring adopts a “distorted chair” conformation with a deviation of 0.682(7) A for the tricoordinated sulfur atom. Remarkably, a short exocyclic S-N bond length 1.489(4) A along with a large P-N-S angle 136.2(3)° are observed with the iminophosphorus moiety.

Crystal structure analysis of (Morpholino)(Phenyl)(Dicyclohexylamino) phosphiniminocyclotrithiazene

REACTIONS OF α,β-UNSATURATED NITRONES DERIVED FROM CHALCONES: ISOLATION OF STABLE YLIDES FORMED ON REACTION WITH DIMETHYL ACETYLENEDICARBOXYLATE

C4a 0.1799 (6) 0.0688 (12) 0.4029 (6) 0.031 C4 0.2133 (7) 0.1846 (12) 0.3415 (6) 0.036 C5 0.1756(6) 0.1858(12) 0.2550(6) 0.035 C6 0.0992 (6) 0.0701 (11) 0.2208 (5) 0.026 C7 0.0606 (6) -0.0530 ( I I ) 0.2801 (6) 0.029 C7a 0.1028 (7) -0.0513 (12) 0.3721 (6) 0.031 C8 0.0810 (9) -0.3182 (15) 0.6577 (7) 0.067 C9 0.2527 (7) 0.3571 (13) 0.5882 (7) 0.049 C10 0.1200 (8) 0.2245 (13) 0.0537 (6) 0.050 Cll 0.0254(8) -0.3734(13) 0.1896(7) 0.049

T. Mohan

Papers

Crystal structure analysis of (N-methyl piperazino) (phenyl) (dicyclohexylamino) phosphiniminocyclotrithiazene

S-[(Dicyclohexylamino)(phenyl)(1-pyrrolidinyl)phosphinimino]cyclotrithiazene

Crystal structure analysis of (Morpholino)(Phenyl)(Dicyclohexylamino) phosphiniminocyclotrithiazene