Ligand Exchange Reactions of Triphospholyl Metal Carbonyl Complexes

Zenneck U, Heinemann FW, Pritzkow H, Zeller M (2001)

Publication Type: Journal article

Publication year: 2001

Journal

Organometallics American Chemical Society

Book Volume: 20

Pages Range: 2905-2915

Abstract

Utilizing 1-triphenylstannyl-3,5-di(tert-butyl)-1,2,4-triphosphole (2) as the transfer reagent for the 1,2,4-triphospholyl ligand, the new cobalt dicarbonyl complex (η⁵-t-Bu2C2P3)(CO) 2Co (4) has been prepared. The reactivity of 4 and that of triphosphacymantrene (η⁵-t-Bu2C2P3) (CO)3Mn (3) toward carbonyl exchange have been investigated. When 3 or 4 are photolyzed in the presence of phosphanes the mono- and disubstituted complexes (η⁵-t-Bu2C2P3)(CO) (PR3)Co (R = Et (5), Ph (6)) and (η⁵-t-Bu2C2P3)(CO) (PMe3)2Mn (7) obtained. In the absence of additional ligands, the irradiation of 3 in n-hexane results in the formation of the dinuclear rac and meso complexes {μ[1:1-5-η-t-Bu2C2P3](CO)2Mn} 2 (8a and 8b). Under thermal conditions the carbonyl ligands of both 3 and 4 are replaced by isonitrile ligands to yield (η⁵-t-Bu2C2P3) (CN-Cy)2Co (9), (η⁵-t-Bu2C2P3)(CO)(CN-Cy)Co (10), and (η⁵-t-Bu2C2P3)- (CO)2(CN-Cy)Mn (11), respectively. The substances have been fully characterized including X-ray structural analysis for the complexes 4, 6, 7, 8a, 8b, and 9. Under both photochemical and thermal conditions the complexes 3 and 4 are much more reactive than their phosphorus-free cyclopentadienyl analogues. In contrast with cymantrene, triphosphacymantrene (3) seems to react via an associative pathway.

Authors with CRIS profile

Ulrich Zenneck Professur für Anorganische Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Ruprecht-Karls-Universität Heidelberg

Germany (DE)

How to cite

APA:

Zenneck, U., Heinemann, F.W., Pritzkow, H., & Zeller, M. (2001). Ligand Exchange Reactions of Triphospholyl Metal Carbonyl Complexes. Organometallics, 20, 2905-2915.

MLA:

Zenneck, Ulrich, et al. "Ligand Exchange Reactions of Triphospholyl Metal Carbonyl Complexes." Organometallics 20 (2001): 2905-2915.

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