The first examples of cyclooctadienylmolybdenum complexes, [MoBr(CO)2(NCMe)2(1–3-η:5,6-C8H11)] and [MoBr(CO)2(NCMe)2(1–3-η:4,5-C8H11)], accessible by reaction of [Mo(CO)3(NCMe)3] with bromocyclooctadienes, are precursors to [MoBr(CO)2(L2)(η3-C8H11)] [L2
= 2,2′-bipyridine; Ph2P(CH2)nPPh2 (n
= 1 or 2); 2CNBut]; [Mo(CO)2(η3-C8H11)Cp], and [Mo(CO)2(L3)(η3-C8H11)]+ (L3
= NCMe or CNBut). The X-ray crystal structures of [MoBr(CO)2(L2)(1–3-η:5,6-C8H11)] (L2
= 2,2′-bipyridine
or Ph2PCH2CH2PPh2) and [Mo(CO)2(CNBut)3(1–3-η:4,5-C8H11)][BF4] have been determined and the solid state conformations of the two types of trihapto-bonded cyclooctadienyl ring investigated. The characteristic 1H and 13C{1H} NMR spectral features of the 1–3-η:5,6-C8H11 and 1–3-η:4,5-C8H11 ligands are defined.
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