Reactions of mer-Mo(H)(CO)(NO)(PMePh2)3 with Ethylene, Propylene, and Styrene That Bear on Alternating CO/Olefin Coupling Chemistry

The tris(diphenylmethyl)phosphine molybdenum complex mer-Mo(Cl)(CO)(NO)(PMePh2)3 (2), prepared by the reaction of 4 equiv of PMePh2 with trans-Mo(ClAlCl3)(NO)(CO)4 (1), undergoes a metathesis reaction with LiBH4 to afford the hydrido nitrosyl complex mer-Mo(H)(CO)(NO)(PMePh2)3 (3). The reactions of...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Organometallics 1997-05, Vol.16 (11), p.2335-2342
Hauptverfasser: Cheng, Tan-Yun, Southern, Joel S, Hillhouse, Gregory L
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:The tris(diphenylmethyl)phosphine molybdenum complex mer-Mo(Cl)(CO)(NO)(PMePh2)3 (2), prepared by the reaction of 4 equiv of PMePh2 with trans-Mo(ClAlCl3)(NO)(CO)4 (1), undergoes a metathesis reaction with LiBH4 to afford the hydrido nitrosyl complex mer-Mo(H)(CO)(NO)(PMePh2)3 (3). The reactions of several olefins (ethylene, propylene, styrene) with 3 have been examined, and these studies have uncovered interesting stoichiometric coupling reactions involving hydride, CO, olefin, acyl, and alkyl ligands which bear on alternating CO/olefin oligomerization chemistry. Reaction of 3 with C2H4 (50 °C, 50 psi, 48 h) results in the loss of a PMePh2 ligand and incorporation of 3 equiv of C2H4 to give trans-Mo{CH2CH2C(O)CH2CH3}(C2H4)(NO)(PMePh2)2 (4) in good isolated yield. A slower reaction is observed between 3 and propylene with incorporation of only one olefin in the metal coordination sphere, giving isomeric mer-Mo{η2-C(O)CH2CH2CH3}(NO)(PMePh2)3 (5) and mer-Mo{η2-C(O)CH(CH3)2}(NO)(PMePh2)3 (6). Treatment of solutions of 5 and 6 with HCl results in their conversion to two new aldehyde complexes, mer-MoCl(η1-OCHCH2CH2CH3)(NO)(PMePh2)3 (7) and mer-MoCl{η1-OCHCH(CH3)2}(NO)(PMePh2)3 (8), respectively. Treatment of 7 and 8 with CO results in their ultimate conversion to Mo(Cl)(CO)2(NO)(PMePh2)2 (11), butyraldehyde, and isobutyraldehyde via the bis(phosphine) aldehyde intermediates trans-MoCl(η1-OCHCH2CH2CH3)(CO)(NO)(PMePh2)2 (9) and trans-MoCl{η1-OCHCH(CH3)2}(CO)(NO)(PMePh2)2 (10). Styrene reacts slowly (5 d, 50 °C) with benzene solutions of 3 to give 1 equiv of ethylbenzene and emerald-green trans-Mo[PMePh{C6H4C(O)CH2CH2C6H4}](NO)(PMePh2)2 (12) in high yield.
ISSN:0276-7333
1520-6041
DOI:10.1021/om970160s