Different Transformation Pathways in the Photolysis of [Cp*P{W(CO)5}2]

Insertion Reactions of Nitriles into the P−C Bond of [(η1-C5Me5)P{W(CO)5}2]—A Novel Approach to Phosphorus-Containing Heterocycles

“…[1] The chemistry of this highly reactive intermediate A offers promising synthetic routes to a large variety of new phosphametallaheterocycles. Thus, the trapping reaction of A with phosphaalkynes [1] and alkynes [2] proceeds by formal [22] cycloaddition reactions to form novel main group element transition metal cage compounds. In continuation of these reactivity studies we attempted to employ nitriles for trapping reactions of intermediate A.…”

“…To avoid the observed insertion reaction and to obtain a [22] cycloaddition product from the intermediate [Cp*(CO) 2 W P 3W(CO) 5 ] A and the C N triple bond of a nitrile, we used exclusively organonitriles without b-hydrogen atoms. However, when tBuCN was used as the trapping reagent in the thermolysis reaction, it was found not to react with 1.…”

“…Besides the formation of the intermediate [Cp*(CO) 2 WP 3W(CO) 5 ] A containing a WÀP triple bond, [1,2] and a Cp* elimination, [22] also an insertion reaction into the unstrained P À C s bond of 1 proceeds under very mild conditions. With benzonitrile as a reaction component an additional CÀH bond activation occurs.…”

Diphosphorus-bridged heterometallic anions and hydrides derived from reactions of complex [Mo2Cp2(μ-PCy2)(μ-κ2:κ2-P2)(CO)2]− with precursors of 16-electron metal carbonyl fragments

“…The only other structurally characterized hydride complex displaying a comparable Mo 2 P 2 tetrahedral core with exocyclic M(CO) 5 fragments appears to be the hydride-bridged tungsten complex [W 4 Cp*(CO) 16 (m-H)(m-k 2 :k 2 :k 1 :k 1 -P 2 )], which is an electron-precise molecule (WeW ¼ 3.1417(9) Å) displaying a significantly longer PeP separation of 2.116(6) Å [17]. Thus, we conclude that the shortening of the PeP bond observed in 5d is somehow associated to the electronic unsaturation of the dimolybdenum centre in this molecule, while the presence of exocyclic W(CO) 5 groups bound to the central M 2 P 2 tetrahedron would have itself no significant elongation effects on that bond.…”

The Complexed Triphosphaallyl Radical, Cation, and Anion Family

“…[23] Compound G is formed by Cp* migration from phosphorus to tungsten with a change in the coordination mode from h 1 to h 5 (Scheme 1). This reaction proceeds primarily under thermolytic conditions, however, photolysis of 1 leads, additionally, to the elimination of a Cp*C moiety and the formation of the radical intermediate H. [24] The electronic structure of H was recently calculated by using DFT methods. [21] We now find that this intermediate acts as a phosphorus-radical-transfer reagent and is responsible for the reaction of 1 with diphosphenes to afford an unprecedented complex of type E.…”