127591-46-2Relevant academic research and scientific papers
Site selectivity studies on heterobimetallic complexes: Substitution reactions of (η5-C5H5)MM′(CO)8 (M = Mo, W; M′ = Mn, Re)
Ingham, Wayne L.,Coville, Neil J.
, p. 4084 - 4090 (2008/10/08)
Synthesis of the heterobimetallic dimers (η5-C5H5)M(CO)3M′(CO) 5 (M = Mo, W; M′ = Mn, Re) has been achieved by photochemical procedures from [(η5-C5H5)M(CO)3]2 and M2(CO)10 (5-10%), by reaction of Na[(η5-C5H5)M-(CO)3] and M′(CO)5X (X = I, Br) (15-25%) and by reaction of Na[(η5-C5H5)M(CO)3] and M′(CO)5CF3SO3 (45-95%). Reaction of (η5-C5H5)MRe(CO)8 (M = Mo, W) with L (L = P(OMe)3, PMe2Ph, PMePH2, PPh3, P(CH2C6H5)3, P([p-C6H4OMe)3, t-BuNC, 2,6-Me2C6H3NC, C6H11NC, C6H5CH2NC) under Me3NO, PdO, and thermal conditions yields (η5-C5H5)MRe(CO)8-nLn (n = 1, 2) (20-90% yield). Cleavage reactions of the substituted product with Br2, performed in an NMR tube (CD3CN), revealed that replacement of CO had occurred on the Re atom. The complexes (n = 1) were obtained as the axial isomer and/or the equatorial isomer and were characterized by IR and NMR spectroscopy. Reaction of (η5-C5H5)MMn(CO)8 (M = Mo, W) with RNC (R = 2,6-Me2C6H3, t-Bu, C6H5H2, C6H11) only gave [(η5-C5H5)M(CO)3]2 and Mn2(CO)10-xRNCx (x = 1-4). Reaction with L (L = P(OMe)3, PMe3, PMe2Ph, PPh3) gave homonuclear dimers as well as (η5-C5H5)MMn(CO)7L in which substitution had occurred on Mn. The results could be interpreted in terms of the steric and electronic requirements of L as well as the steric requirements of the metal fragments. An analysis of the spectra of the new (η5-C5H5)MM′(CO)7L complexes revealed that Δ(31Pax-eq), i.e., the difference in 31P positions for axial and equatorial isomers, gave a measure of the steric size of the metal fragments.
Pd-catalysed carbonyl ligand substitution reactions of and by isocyanides
Coville, Neil J.,Johnston, Peter,Leins, Ann E.,Markwell, Anthony J.
, p. 401 - 420 (2007/10/02)
The Pd-catalysed carbonyl ligand displacement reactions of , (M=Mn, Re) with isocyanides to yield the substituted derivatives , (x=1-5, R=Me, i-Pr, t-Bu, C6H5CH2, C6H11, C6H3Me2-2,6), and Br, (x=5,6, R=t-Bu, C6H
