| 15683808 |
Xu Z, Butler IS, Mayr A: The pressure tunning Raman and IR spectral studies on the multinuclear metal carbyne complexes. Spectrochim Acta A Mol Biomol Spectrosc. 2005 Mar;61(5):995-1000.
The Raman and infrared (IR) spectra of four tungsten metal carbyne complexes I, II, IV and V [Cl (CO) 2 (L) W [triple bond] CC6H4 [triple bond](C [triple bond] CC6H4) n [triple bond] N [triple bond] C [triple bond]] 2M (L = TMEDA, n = 0, M = PdI2 or ReCl (CO) 3; L = DPPE, n = 1, M = PdI2 or ReCl (CO) 3) were studied at high external pressure. Their pressure-induced phase transitions were observed near 20kbar (complexes I), 15 kbar (complexes II), 25 kbar (complex IV) and 30 kbar (complex V). The pressure-induced phase transition likely is first order in complex I and the pressure-induced phase transitions of complexes II, IV and V are mostly second order. The pressure sensitivities d nu/dp of nu (W [triple bond] C) are high in the low-pressure phase area and very low in the high-pressure phase area due to the pressure strengthening pi back-bonding from metal W to pi* orbital of C [triple bond] O in fragment Cl (CO) 2 (L) W [triple bond] C. The pressure strengthening metal pi back-bonding from metal Re or Pd to pi* orbital of C [triple bond] O or C [triple bond] N also happened to both of central metal centers of NCPd (I2) CN in complex I and NCReCl (CO) 3CN in complex II. |
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