The chemistry of new cyclic phosphorus(III) ligands

A range of new aniline derivatives of tetrakis(hydroxymethyl)phosphonium chloride represented as [P(CH2NHR)4]Cl, where R = phenyl or a substituted phenyl group were synthesised by reacting tetrakis(hydroxymethyl)phosphonium chloride with different aniline precursors in EtOH. Similarly, new phenylenediamine derivatives of tetrakis(hydroxymethyl)phosphonium chloride [P{(CH2NHhRh]Cl, [R = C614, C6H3Me, C6H3COPh, C6H2C414] were synthesised by reacting tetrakis(hydroxymethyl)phosphonium chloride with phenylenediamine precursors. Selected aniline derivatives of tetrakis(hydroxymethyl)phosphonium chloride were reacted with triethylamine in acetone at room temperature to give the corresponding diazaphosphorinane ligands cyclo- {CH2N(R)CH2N(R)CH2-P}-CH2N(H)R , where R = phenyl or a substituted phenyl group. Some of the diazaphosphorinane ligands were reacted with Ru(II), Rh(III), Ir(III) , Pd(lI) and Pt(lI) precursors to form new transition metal complexes... cont'

Intramolecular hydrogen-bonded tertiary phosphines as 1,3,5-triaza-7-phosphaadamantane (PTA) analogues

New cationic trialkylphosphines [P(CH2NH2R){CH2N(R)CH2N(R)CH2}]+ (R ) C6H5CH2, a; 4-FC6H4CH2, b), as their Cl- (1a, 1b), SbF6 - (2a, 2b), and PF6 - (3a, 3b) salts, are described. The phosphine framework is conformationally locked, in the solid state, through pairs of intramolecular N-H · · · N hydrogen bonds which are maintained in the RuII and RhIII complexes 4 and 5. Phosphines 1a-3b can be considered as charged variants of the well-known PTA ligand

Unusual metal-coordinated zwitterionic P-C-N-C-N-C phosphido adducts

Rare examples of homodinuclear zwitterionic PdII and PtII complexes with bridging, two-coordinate P{cyclo-CH2N(R)CHN- (R)CH2} ligands (R = 4-FC6H4CH2, C6H5CH2) have been characterized by single-crystal X-ray diffraction using synchrotron radiation. Short N-C distances and enlarged N-C-N bond angles support electron delocalization in the central N-C-N backbone

Synthesis and characterization of new tetraalkylaminophosphonium chlorides

<p>New tetraalkylaminophosphonium chlorides were readily prepared by four-fold condensation of commercially available [P(CH₂OH)₄]Cl with a range of fifteen aryl based primary amines, in EtOH, at ambient temperature. All compounds have been characterized by FT–IR spectroscopy and elemental analysis. Solution ³¹P{¹H} NMR studies of these chloride salts reveal their instability with respect to various P^III/P^V species. The structures of three examples have been determined by single crystal X-ray diffraction and confirm the pseudotetrahedral arrangement around the P^V center. Extensive N–H···Cl hydrogen bonding is observed.</p