Tungsten phosphido complexes

To prevent the latter mentioned subsequent reactions, the bulky phos-phaalkyne Ph C P as well as tungsten alkoxides of reduced size as, e.g., [W2(ONp)6] were employed in these three-component reactions with no significant success [15]. The crucial steps for the side-product free synthesis of the phosphido complexes 18 are the introduction of a phosphaalkyne possessing a moderate steric bulkiness, which lies between those of f-BuC=P and Ph C P, and resulting from the P-NMR studies (cf. Eq. 5), a reaction temperature mode allowing the complete metathesis reaction to take place at very low temperatures over a long period of time until all the phosphaalkyne has been converted into the metathesis products (about 12 h) only then is the reaction mixture allowed to reach room temperature. We found that MesC=P meets these steric requirements, and the three-component-reaction between MesC=P, [W2(Of-Bu)6] and [M(CO)5(thf)] (M = Cr, W), carried out at -78 °C and warmed up to ambient temperature within 15 h, succeeded in the synthesis and isolation of the phosphido complex 18a,b (Scheme 2) [15]. Furthermore, if t-BuC=P is incorporated into these reactions, the steric requirements of the alkoxide dimer has to be slightly increased. Thus, f-BuC=P reacts with [W2(OPh )6] and [M(CO)5(thf)] (M=Cr, W) under the... 

Trialkoxy complexes of tungsten with terminal phosphido ligands could not yet be isolated. They were postulated to be very reactive intermediates in different transformation reactions, e.g., during the metathesis reaction of [W2(0R)6] with phosphaalkynes [6, 14]. However, we were able to characterize the complex [(t-BuO)3W=P] (3c) by P-NMR spectroscopy by monitoring the metathesis reaction of [W2(Ot-Bu)6] with MesC=P in the tempera-... 

The synthesis of Fe-Mo and Fe-W dinuclear complexes is often assisted by bridging phosphido ligands, although it is also known that a number of tungsten acetylides " and related complexes " provide effective building blocks for the creation of heterobimetallic Fe-W complexes. 

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