Silicon—phosphorus bonds

A number of exchange reactions of di-t-butyl(trimethylsilyl)phosphine (62) have been described.64-67 They generally involve cleavage of the silicon-phosphorus bond of (62), and a selection is outlined in Scheme 6. 

Dimethyl(trimethylsilyl)phosphine (63) reacts with aluminium chlorides with cleavage of the silicon-phosphorus bond,58 as shown for aluminium trichloride. The same phosphine (63) reacts with the cobalt derivative (64) as shown.59... 

A silicon-phosphorus bond in (Me2PSiMe)3 is readily cleaved by methyl-lithium to generate the acyclic dilithiated derivative Me2Si(PLiMe)2 [10.36, eqn (10.26)]. The related dilithiated dianion Me2Si(PLi Bu)2 has been used to... 

Element-element bonds, addition to G-G multiple bonds arsenic—selenium bonds, 10, 782 boron—boron bonds, 10, 727 boron—sulfur bonds, 10, 778 B-S and B-Ge bonds, 10, 758 chalcogen—chalcogen additions, 10, 752 germanium—germanium bonds, 10, 747 germanium-tin bonds, 10, 780 overview, 10, 725-787 phosphorus—phosphorus bonds, 10, 751 phosphorus—selenium bonds, 10, 782 phosphorus-sulfur bonds, 10, 781 Se-Si and Se-Ge bonds, 10, 779 silicon-germanium bonds, 10, 770 silicon-phosphorus bonds, 10, 780 silicon-silicon bonds, 10, 734 silicon-sulfur bonds, 10, 779 silicon-tin bonds, 10, 770 tin-boron bonds, 10, 767 tin-tin bonds, 10, 748... 

The direct silicon-phosphorus bond coupling constant (/P Si 115-Hz, CH2C12, -60°C) was observed for the complex shown in Eq. (47) (225). Selected complexes for which the silylonium structure in solids or in solution was proved are collected in Table IV (see also Refs. 269 and 270). 

To promote the formation of the rather weak silicon-phosphorus bonds, we have introduced anionic monophosphinomethanide and diphosphinomethanide ligands of type I or II (Fig. 1), respectively, into the coordination sphere of a silicon center. 

Recently the reductive trichlorosilylation of chlorophosphanes with hexachlorodisilane provided a novel, mild access to molecules with silicon-phosphorus bonds [1-4], Dialkylchlorophosphanes and dialkylamino(alkyl)chlorophosphanes were easily converted into trichlorosilylphosphanes. 

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