189567-39-3Relevant academic research and scientific papers
Reactions of mer-Mo(H)(CO)(NO)(PMePh2)3 with ethylene, propylene, and styrene that bear on alternating CO/olefin coupling chemistry
Cheng, Tan-Yun,Southern, Joel S.,Hillhouse, Gregory L.
, p. 2335 - 2342 (2008/10/08)
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(C1A1C13)(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}(C 2H4)(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{n2-C(O)CH2CH2CH 3}(NO)(PMePh2)3 (5) and mer-Mo{n2-C(O)CH(CH3)2(NO)(PMePh 2)3 (6). Treatment of solutions of 5 and 6 with HCl results in their conversion to two new aldehyde complexes, mer-MoCl(η1-O=CHCH2CH2CH 3)(NO)(PMePh2)3 (7) and mer-MoCl{n1-O=CHCH(CH3)2}(NO)(PMePh 2)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=CHCH2CH2CH 3)(CO)(NO)(PMePh2)2 (9) and trans-MoCl-{n1-O=CHCH(CH3)2}(CO)(NO)(PMePh 2)2 (10). Styrene reacts slowly (5 d, 50 °C) with benzene solutions of 3 to give 1 equiv of ethylbenzene and emerald-green frans-Mo[PMePh-{C6H4C(O)CH2CH2C 6H4}](NO)(PMePh2)2 (12) in high yield.
