Phosphanediyl Transfer from Inversely Polarized Phosphaalkenes R1P=C(NMe2)2 (R1 = tBu, Cy, Ph, H) onto Phosphenium Complexes [(η5‐C5H5)(CO)2M=P(R2)R3] (R2 = R3 = Ph; R2 = tBu, R3 = H; R2 = Ph, R3 = N(SiMe3)2) Reaction of the freshly prepared phosphenium tungsten complex [(η5‐C5H5)(CO)2W=PPh2] (3) with the inversely polarized phosphaalkenes RP=C(NMe2)2 (1) (a: R = tBu; b: Cy; c: Ph) led to the η2‐diphosphanyl complexes $\rm [(\eta^{5}-C_{5}H_{5})(CO)_{2}\overline {W-P(R)-P}Ph_{2}]$ (9a‐c) which were isolated by column chromatography as yellow crystals in 24‐30 % yield. Similarly, phosphenium complexes [(η5‐C5H5)(CO)2M=P(H)tBu] (M = W (6); Mo (8)) were converted into $\rm [(\eta^{5}-C_{5}H_{5})(CO)_{2}\overline {MP({\it t}Bu)P}(H){\it t}Bu]$ (M = W (11); Mo (12)) by the formal abstraction of the phosphanediyl [PtBu] from 1a. Treatment of [(η5‐C5H5)(CO)2W=P(Ph)N(SiMe3)2] (4) with HP=C(NMe2)2 (1d) gave rise to the formation of yellow crystalline $\rm [(\eta^{5}-C_{5}H_{5})(CO)_{2}\overline {W-P(H)-P} (Ph)N(SiMe_{3})_{2}]$ (10). The products were characterized by elemental analyses and spectra (IR, 1H, 13C‐, 31P‐NMR, MS). The molecular structure of compound 10 was elucidated by an X‐ray diffraction analysis.

The reaction of the vinylidene complexes [(C5H5)(CO)(NO)W=C=C(H)R] (10a: R = tBu; 10b: R = Ph) with the arsaalkene tBuC(O)–As=C(NMe2)2 (11) afforded the novel η2‐1‐arsaallene complexes [η2‐{tBuC(O)–As=C=C(H)R}W(CO)(NO)C5H5] (13: R = tBu; 15: R = Ph). Similarly, treatment of 10a with the ferrioarsaalkene [(C5Me5)(CO)2Fe–As=C(NMe2)2] (12) led to the formation of [η2‐{[(C5Me5)(CO)2Fe]–As=C=C(H)tBu}W(CO)(NO)(C5H5)] (14), whereas combination of 12 and 10b yielded the carbene complex [(C5H5)(CO)(NO)W=C(NMe2)C(Ph)=C(H)NMe2] (16) in high yield instead of the anticipated arsaallene complex. The novel compounds 13, 14, 15 and 16 were characterised by elemental analyses and by means of spectroscopy (IR, 1H, 13C NMR). Moreover, the molecular structures of 14 and 15 were elucidated by X‐ray diffraction analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

The reaction of the vinylidene complex [(η5‐C5H5)(CO)(NO)W=C=C(H)Ph] (9) with the phosphaalkenes RP=C(NMe2)2 (1a: R = tBu; 1c: R = c‐C6H11) affords the novel η2‐1‐phosphaallene complexes [η2‐{RP=C=C(H)Ph}W(CO)(NO)(η5‐C5H5)] (14: R = tBu; 15: R = c‐C6H11) in addition to the carbene complex [(η5‐C5H5)(CO)(NO)W=C(NMe2)C(Ph)=C(H)NMe2] (16). Similarly, treatment of [(η5‐C5H5)(CO)(NO)W=C=CH2] (12) with the phosphaalkenes gives rise to the formation of [η2‐{RP=C=CH2}W(CO)(NO)(η5‐C5H5)] (17: R = tBu; 18: R = c‐C6H11). The novel compounds 14, 15, 17, and 18 were characterized by elemental analysis and by spectroscopy (IR, 1H, 13C NMR, MS). Moreover, the molecular structures of 14 and 16 were determined by X‐ray diffraction analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

No abstract

Reaction of [(η5‐C5H5)(CO)2M=P=C(SiMe3)2] [where M = Mo (2), W (5)] with the phosphaalkene tBuP=C(NMe2)2 (1a) afforded the η3‐1,2‐diphosphaallyl complexes [(η5‐C5H5)(CO)2M{η3‐tBuPPC(SiMe3)2}], [where M = Mo (3a); M = W (6)]. Similarly, 2 and CyP=C(NMe2)2 (1b; where Cy = cyclohexyl) gave rise to the formation of [(η5‐C5H5)(CO)2Mo{CyPPC(SiMe3)2}] (3b) by a phosphinidene transfer process. Small amounts of [{η5‐C5H5)(CO)2Mo}2{η2:η2‐Cy3P5}] (4) were formed as a minor product. However, treatment of 2 and 5 with HP=C(NMe2)2 (1c) yielded the complexes [(η5‐C5H5)(CO)2M{η2‐(Me3Si)2CH–P=P–C(NMe2)2}] [where M = Mo (9), W (10)]. The novel compounds 3a, 3b, 9 and 10 were characterized by means of spectroscopy (IR, 1H, 13C{1H}, 31P{1H} NMR, MS). Moreover, the molecular structures of 3a, 3b, 4, 6 and 10 were determined by X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)