PUB - Publikationen an der Universität Bielefeld

Reaction of ClP=C(SiMe(2)iPr)(2) (3) with Na[MO(CO)(3)-(eta(5)-C5H5)] afforded the phosphavinylidene complex [(eta(5)-C5H5)(CO)(2)Mo=P=C(SiMe(2)iPr)(2)] (4) which in situ was converted into the eta(1)-1,2-diphosphaallyl complex [eta(5)-(C5H5)(CO)(2)Mo{eta(3)-tBuPPC(SiMe(2)iPr)(2)] (6) by treatment with the phosphaalkene tBuP=C(NMe2)(2). The chloroarsanyl complexes [(eta(5)-C5H5)(CO)(3)M - As(Cl)CH(SiMe3)(2)] [where M=Mo (9); M=W (10)] resulted from the reaction of Na[M(CO)(3)(eta(5)-C5H5)] (M= Mo, W) with Cl2AsCH(SiMe3)(2). The tungsten derivative 10 and Na[CO(CO)(4)] underwent reaction to give the dinuclear mu-arsinidene complex [(eta(5)-C5H5)(CO)(2)W - CO(CO)(3){mu-AsCH(SiMe3)(2)}(mu-CO)] (11). Treatment of [(eta(5)-C5H5)(CO)(2)Mo{eta(3)-tBuPPC(SiMe3)(2)}] (1) with an equimolar amount of ethereal HBF4 gave rise to a 85/15 mixture of the saline complexes [(eta(5)-C5H5)(CO)(2)Mo{eta(2)-tBu(H)P - P(F)CH(SiMe3)(2)}]BF4 (18). and [Cp(CO)(2)MO{F2PCH(SiMe3)(2)}(tBuPH(2))]BF4 (19) by HF-addition to the PC bond of the eta(3)-diphosphaallyl ligand and subsequent protonation (18) and/or scission of the PP bond by the acid (19). Consistently 19 was the sole product when I was allowed to react with an excess of ethereal HBF4. The products 6, 9, 10, 11, 18 and 19 were characterized by means of spectroscopy (IR, H-1-, C-13{H-1}-, P-31{H-1}-NMR, MS). Moreover, the molecular structures of 6, 11 and 18 were determined by X-ray diffraction analysis.