Zusammenfassung
The reaction of the phosphinidene complex [Cp*P{W(CO)(5)}(2)] (1a) with diphenyldiazomethane leads to [{W(CO)(5)}Cp*P=NN{W(CO)(5)}=CPh2] (2). Compound 2 is a rare example of a phosphadiazadiene ligand (R-P=N-N=CRR) complex. At temperatures above 0 degrees C, 2 decomposes into the complex [{W(CO)(5)}PCp*{N(H)N=CPh2)(2)] (3), among other species. The reaction of the pentelidene complexes ...
Zusammenfassung
The reaction of the phosphinidene complex [Cp*P{W(CO)(5)}(2)] (1a) with diphenyldiazomethane leads to [{W(CO)(5)}Cp*P=NN{W(CO)(5)}=CPh2] (2). Compound 2 is a rare example of a phosphadiazadiene ligand (R-P=N-N=CRR) complex. At temperatures above 0 degrees C, 2 decomposes into the complex [{W(CO)(5)}PCp*{N(H)N=CPh2)(2)] (3), among other species. The reaction of the pentelidene complexes [Cp*E{W(CO)(5)}(2)] (E=P, As) with diazomethane (CH2NN) proceeds differently. For the arsinidene complex (1b), only the arsaalkene complex 4b [{W(CO)(5)}(2){(1:2)-(Cp*)As=CH2}] is formed. The reaction with the phosphinidene complex (1a) results in three products, the two phosphaalkene complexes [{W(CO)(5)}(2){(1:2)-(R)P=CH2}] (4a: R=Cp*, 5: R=H) and the triazaphosphole derivative [{W(CO)(5)}P(Cp*)-CH2-N{W(CO)(5)}=N-N(N=CH2)] (6a). The phosphaalkene complex (4a) and the arsaalkene complex (4b) are not stable at room temperature and decompose to the complexes [{W(CO)(5)}(4)(CH2=E-E=CH2)] (7a: E=P, 7b: E=As), which are the first examples of complexes with parent 2,3-diphospha-1,3-butadiene and 2,3-diarsa-1,3-butadiene ligands.
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