Side-on bound dinitrogen complex of zirconium supported by a P2N2 macrocyclic ligand.

Reduction of [P 2N 2]ZrCl 2 (where P 2N 2 = PhP(CH 2SiMe 2NSiMe 2CH 2) 2PPh) by KC 8 under N 2 generates the dinuclear dinitrogen complex ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2) and impurities in varying yields depending on the solvent and temperature. The toluene complex [P 2N 2]Zr(eta (6)-C 7H 8) along with a dinuclear species with bridging PC 6H 5 groups is observable. Also observable in the crude reaction mixtures is the mu-oxodiazenido derivative, ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2H 2)(mu-O), due to reaction with trace H 2O.

Formation of phosphorus-nitrogen bonds by reduction of a titanium phosphine complex under molecular nitrogen.

The reduction of high oxidation state metal complexes in the presence of molecular nitrogen is one of the most common methods to synthesize a dinitrogen complex. However, the presence of strong reducing agents combined with the poor binding ability of N2 can lead to unanticipated outcomes. For example, the reduction of [NPN]ZrCl2(THF) (where NPN = PhP(CH2SiMe2NPh)2) with KC8 under N2 leads to the formation of the side-on bridged dinuclear dinitrogen complex ([NPN]Zr(THF))2(mu-eta2:eta2-N2) with an N-N bond distance of 1.

Carbon-nitrogen bond formation via the reaction of terminal alkynes with a dinuclear side-on dinitrogen complex.

The dinuclear dinitrogen complex ([P2N2]Zr)2(mu-eta2:eta2-N2) reacts with terminal aryl alkynes to generate a new species in which the dinitrogen unit has been functionalized. The products formed have the general formula ([P2N2]Zr)2(mu-eta2:eta2-N2CCAr)(mu-CCAr) and display a styryl-hydrazido unit bridging the two Zr centers along with a bridging arylalkynide. The crystal structures of three of these products are reported.

Side-on bridging coordination of N2: spectroscopic characterization of the planar Zr2N2 core and theoretical investigation of its butterfly distortion.

The vibrational and electronic structure of the side-on N(2)-bridged Zr complex [((P(2)N(2))Zr)(2)(mu-eta(2):eta(2)-N(2))] (P(2)N(2)=PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh) were analyzed. The vibrational characterization of the planar Zr(2)N(2) core was based on resonance Raman and infrared spectroscopy. In the Raman spectrum, the Nbond;N stretching band is found at 775 cm(-1) with an isotope shift of 22 cm(-1).

Phosphorus phenyl-group activation by reduced zirconium and niobium complexes stabilized by the [P2N2] macrocycle.

Reduction of [P2N2]ZrCl2 (where [P2N2] = PhP(CH2SiMe2NSiMe2CH2)2PPh) with KC8 under argon generates the phosphorus phenyl bridged bimetallic complex where the bridging phenyl groups are formally reduced to bis(allyl) dianions. Similar reduction of [P2N2]NbCl caused the one-electron reduction of the phosphorus phenyl group to generate a cyclohexadienyl moiety via a C-C bond formation between the ipso carbons of the two phenyl groups.