Journal article

Publication year: 2005

Pages: 206-213

Journal: Organometallics

Volume number: 24

Issue number: 2

ISSN: 0276-7333

DOI Link: https://doi.org/10.1021/om0493715

Publisher: American Chemical Society

Abstract: 
Reaction of a dilute solution of LiC=CP(C6H5)(2) (5) with the tungsten carbonyl complex (eta(5) -CP)(CO)(2)(NO)W (1a) afforded at -30 degreesC after protonation the bimetallic complexes [{(Ph2P)HC=C}(NO)(eta(5)-Cp)(NO)(CO){C=CH(PPh2)}] (8a,b). It could be shown that prior to the formation of 8a,b the eta(1)-vinylidene complex (eta(5)-Cp)(CO)(2)(NO)W=C=CH(PPh2) (7) is formed as an intermediate, which reacts with an additional eta(1)-vinylidene complex 7 present in the solution to give the observed products by losing 1 mol of carbon monoxide. The eta(1)-vinylidene complex 7 and its analogous derivative (eta(5)-Cp)(CO)(2)(NO)W=C=CH(PMeS2) (10; Mes = 2,4,6-trimethylbenzene) are stable in solution at -60 degreesC and could be identified by spectroscopic methods. The eta(1)-vinylidene complexes 7 and 10 are trapped with (eta(5)-Cp)- (CO)(2)(NO)W=C=CHR (R = H (12a), C6H5 (12b), CH3C6H4 (12c)) to give the corresponding bimetallic complexes 13a-c and 14a-c. A different mode of reaction is observed, when the acetylide 5 is treated with a concentrated solution of tungsten carbonyl complex la. Here after protonation the eight-membered bimetallic complex 15 is obtained. The crystal structures of bicyclic complexes 8a, 11, and 13a as well as the monocyclic complex 15 are reported.

Harvard Citation style: Ipaktschi, J., Munz, F. and Klotzbach, T. (2005) Phosphorus-substituted η¹-vinylidene tungsten complexes:: Synthesis and cyclization, Organometallics, 24(2), pp. 206-213. https://doi.org/10.1021/om0493715

APA Citation style: Ipaktschi, J., Munz, F., & Klotzbach, T. (2005). Phosphorus-substituted η¹-vinylidene tungsten complexes:: Synthesis and cyclization. Organometallics. 24(2), 206-213. https://doi.org/10.1021/om0493715