Replacement of metals by phosphorus

Aromatic phosphines that are difficult to obtain by other methods can be prepared by heating alkali phosphides with arenesulfonic acid salts, best in ethylene glycol ethers  

1 -Naphthyldiphenylphosphine 360 Potassium (7.8 g) is dispersed in dry 1,2-diethoxyethane (250 ml) by means of a vibrator and treated dropwise under nitrogen with (chloro)diphenyl-phosphine (21.5 g). After 1 hours warming at 65° the resulting deep red solution is treated with completely dried sodium 1-naphthalenesulfonate (23 g) and heated at 180° for 3 h, whereupon the color fades. The mixture is allowed to cool and hydrolysed carefully with water (100 ml). The ethereal layer is dried and evaporated and the residue is heated on a water-bath with methanol. This leaves the tertiary phosphine undissolved (23.8 g, 75%), m.p. 124°. 

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Replacement of metals by phosphorus by means of elemental phosphorus... 

In the complexes of similar type such as [HRu3(CO)g (CH=C=CNMe2)] there is a hindered rotation about the C-N bond, the barrier of which has a distinct dependence upon the replacement of CO by phosphorus(III) ligands at a distant metal atom. Since steric effects are unlikely to be important the transmittance of electronic effects through the cluster is discussed.Rotation about C-N in the complexes [HFe3(CO)9(CNR2)] is also restricted and an nmr study has been made. ° ... 

Chemical modification of the ALPOs is required to create a new class of catalysts. In the metalloaluminophosphates (MeALPOs), the framework contains metal (Me), aluminium and phosphorus. Thus, it becomes possible to produce a wide range of active catalysts with Lewis and Bronsted acid sites and redox properties by the partial replacement of Al3+ by Me2+ ions (e.g. Co, Cu, Mg, Zn, etc.) in an ALPO framework (Thomas, 1995 Martens etal, 1997). 

It is a challenge to study dimetalated derivatives of primary phos-phanes that possess more covalent metal-phosphorus bonds. This can be achieved through replacement of the alkali metal ions in bimetallic phosphandiides by monovalent coin metal centers. 

Replacement of the hydrogen atoms by methyl groups to give trimethylphosphine (CH3)3P, makes it a stronger base (as [(CH3)3PH]OH), and improves the donor power of the phosphorus as it does with nitrogen. Towards some transition metal atoms or ions, trimethylphosphine is a stronger ligand than ammonia, i.e. forms more stable complexes. This is because the transition metal... 

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