- Reactions of coordinated dinitrogen. 14. Formation of carbon-nitrogen bonds from bis(dinitrogen) complexes of molybdenum
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The single diastereomer trans-Mo(N2)2((S,S)-Chiraphos)2, where (S,S)-Chiraphos is (-)-(2S,3S)-bis(diphenylphosphino)butane, reacted with racemic 2-bromooctane to form MoBr(NNCH(CH3)C6H13)((S,S)-Chiraphos) 2, in which there was a ca. 10% excess of one enantiomer over the other, on the basis of the 1H NMR spectra at 100, 200, and 396 MHz. The 1,4-dihaloalkanes 1-bromo-4-chloro- and 1,4-dibromobutane and 1,4-dibromopentane reacted with trans-Mo(N2)2(dppe)2, where dppe is bis(diphenylphosphino)ethane, to form the corresponding cyclic hydrazido(2-) complex. In the first example bromine rather than chlorine bonded to molybdenum. In the last example cyclization resulted in a nitrogen atom becoming bonded to primary and secondary carbon atoms. Methyl fluorosulfonate and iodomethane alkylated MoBr(NNC4H9)(dppe)2 to form the unsymmetrically substituted hydrazido(2-) complex [MoBr(NN(CH3)C4H9(dppe)2] +. Primary alkyl bromides did not undergo this reaction.
- Bossard, Gerald E.,Adrian George,Lester, Richard K.,Tisdale, Robert C.,Turcotte, Robert L.
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p. 1129 - 1132
(2008/10/08)
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