Abstract
Dinitrogen-bridged complexes of trans-[ReCl(N2)(PMe2Ph)4] with NbCl5 and TaCl5(1 : 1 adducts) and ZrCl4(2 : 1 adduct) have been characterised and a corresponding complex of HfCl4 observed in solution. Nitrogen-15 chemical shifts are compared for three types of dinitrogen bridge: complexes of Mo, W, Re, and Os with a main-group acceptor (AlMe3), complexes of trans-[ReCl(N2)(PMe2Ph)4] with a π acceptor (TiCl4, ZrCl4, HfCl4, NbCl5, or TaCl5), and symmetrical transition-metal complexes, [{W(N2)2(PR2Ph)3}2(µ-N2)](R = Et or Prn), [{Ru(NH3)5}2(µ-N2)]4+, etc. The variation in the shielding is related by simple molecular orbital arguments to the variation in electronic (charge-transfer) absorption, to the periodicities observed for mononuclear dinitrogen complexes, and to the activation of dinitrogen by co-ordination.
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