AN ALLYL(CARBORANE)NITROSYL MOLYBDENUM COMPLEX - PREPARATION AND REACTIVITY

Treatment of CH2Cl2 solutions of [NEt4][closo-3-(eta3-C3H5)-3,3-(CO)2-3,1,2-MoC2B9H11] with [NO][BF4] at room temperature affords the allyl(carborane)nitrosyl complex [closo-3-(eta3-C3H5)-3-(CO)-3-(NO)-3,1,2-MoC2B9H11] in moderate yield. Reaction between the latter compound and K-Selectride (K[BH(Bu(s))3]) in thf, followed by the addition of [N(PPh3)2]Cl affords the eta2-alkene complex [N(PPh3)2][Closo-3-(eta2-CH2=CHMe)-3-(CO)-3-(NO)-3,1,2-MoC2B9H11]. Similarly, the complex [N(PPh3)2][closo-3-(eta2-CH2=CHEt)-3-(CO)-3-(NO)-3,1,2-MoC2B9H11] is obtained from the reaction between [closo-3-(eta3-C3H5)-3-(CO)-3-(NO)-3,1,2-MoC2B9H11] and methyl lithium, followed by the addition of [N(PPh3)2]Cl. Treating CH2Cl2 solutions of the allyl-nitrosyl complex with the nucleophiles PPh3 and Ph3P=CHC(O)Me affords the complexes [closo-3-(eta2-CH2=CHCH2PPh3)-3-(CO)-3-(NO)-3,1,2-MoC2B9H11] and [closo-3-{eta2-CH2=CH CH2CH(PPh3)C(O)Me}-3-(CO)-3-(NO)-3,1,2-MoC2B9H11], respectively. The IR and NMR data (H-1, B-11{H-1}, C-13{H-1} and P-31{H-1}) for the new complexes are reported and discussed in relation to their structures.