The chemistry of cyclopentadienyl nitrosyl and related complexes of molybdenum,part 10(1). Cationic allyl complexes and attack thereon by nucleophiles |
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Authors: | Jon A McCleverty Alan J Murray |
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Institution: | (1) Chemistry Department, The University, S3 7HF Sheffield, UK |
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Abstract: | Summary The syntheses of Mo(5-C5H5)(3-C3H4R)(CO)(NO)]+ (R=H, 1- or 2-Me) and Mo(5-C5H5)(3-C3H5)(NCR)(NO)]+ (R=Me or Ph), by treatment of Mo(5-C5H5)(CO)2(NO) with RC3H4Br and Ag+, and of Mo(5-C5H5)(3-C3H5)(NO)I with Ag+ in the presence of RCN, is described. Treatment of these cations with nucleophiles gives Mo(5-C5H5)(3-C3H5)(NO)X (X=halide, NCS or NCO), Mo(5-C5H5)(3-C3H5Q)(CO)(NO) (C3H5Q= propene ligand, Q= H, SCOMe, SEt, S2CNMe2, S2CNEt2, S2CN(Bu-n)2, C5H5, acac, OH, OMe or OAc), and Mo(5-C5H5)(2C3H5L)(CO)(NO)]+ (L=PEt3, n-Bu3P, PPh3, PPh2H, PMe2Ph, C5H5N, 1-, 3- or 4-MeC5H4N and Me2NNH2). Reaction of Mo(5-C5H5)(3-C3H5)(NCMe)(NO)+ with pyridine gave Mo(5-C5H5)(3-C3H5)(pyr)(NO)]+, while treatment of Mo(5-C5H5)(3-C3H5)(CO)(NO)]+ with PPh3 in the presence of NaOEt afforded Mo(5-C5H5)(CO)(NO)(PPh3). The1H and13C n.m.r. spectra of these complexes are discussed particularly in relation to the occurrence ofexo andendo isomers of the allylic species. Comparison is made briefly between Mo(5-C5H5)(3-C3H5)(NO)I and Mo(C5H5)2(NO)I. |
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