loading . . . Molecular Phosphide Complexes of Zirconium Molecular ZrIV phosphides are extremely rare, with no examples containing a one-coordinated and terminal triple-bonded phosphorus atom. We report here an isolable and relatively stable Zr phosphide complex, [(PN)2Zrā”P{Ī¼2-Na(OEt2)}]2 (4), stemming from a cyclometalated Zr-hydride, [(PN)(PNā²)Zr(H)] (2), and NaPH2. Complex 2 is prepared from two- or one-electron reductions of precursors [(PN)2ZrCl2] (1) or metastable ZrIII[(PN)2ZrCl], respectively. Oxidation of 2 with ClCPh3 (2 equiv) or I2 (1 equiv) resulted in re-formation of the PN ligand and isolation of the ZrIV complexes [(PN)2ZrX2] (X = Cl, 1; X = I, 3), whereas addition of a weak acid to 2 allowed us to intercept the hydrido-halide intermediate [(PN)2Zr(I)(H)] (X = Cl, I) spectroscopically before conversion to 1 or 3. Complex 2 exchanged with D2 (1 atm) to fully deuterate the methylene all ortho-methyl groups of the PN and PNā² ligands and the hydride. Discrete salts of 4 can be readily prepared from Na+ encapsulation with the crown ether 1,4,7,10,13,16-hexaoxacyclooctadecane (18-C-6) or cryptand 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (222-Kryptofix) to form [Na(18-C-6)(THF)2][(PN)2Zrā”P] (5) and [Na(222-Kryptofix)][(PN)2Zrā”P] (6), respectively, which were structurally and spectroscopically characterized. Compounds 4ā6 demonstrate exceptionally short Zrā”P bonds (4, 2.3270(18) Ć
; 5, 2.291(3) Ć
; 6, 2.2989(17) Ć
) and highly downfield 31P NMR spectral resonances (4, 819 ppm; 5 and 6, 927 and 955 ppm) in accord with a terminal phosphide ligand. The Zrā”P motif in 4ā6 can be stabilized via coordination to a softer Tl+ ion to form a nonsolvated phosphide [(PN)2Zrā”P{Ī¼2-Tl}]2 (7), exhibiting a phosphide resonance at ā¼711 ppm. https://pubs.acs.org/doi/10.1021/jacs.4c13935?utm_source=SendGrid_ealert&utm_medium=ealert&utm_campaign=ASAP_jacsat_v0_i0
