C-13 MAGNETIC-RESONANCE SPECTRA OF DIAMAGNETIC CYANO COMPLEXES

被引:65
作者
PESEK, JJ [1 ]
MASON, WR [1 ]
机构
[1] NO ILLINOIS UNIV,DEKALB,IL 60115
关键词
D O I
10.1021/ic50194a006
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Fourier transform 13C NMR spectra are reported for 19 diamagnetic cyano complexes in D2O solution. Data are included for M(CN)6n- complexes of nd6 electron configuration where M=Fe(II), Ru(II), Os(II), Co(III), Rh(III), Ir(III), Pd(IV), or Pt(IV); square-planar M(CN)4n- complexes of nd8 configuration where M=Ni(II), Pd(II), Pt(II), or Au(III); tetrahedral M(CN)4n- complexes of nd10 configuration where M=Cu(I), Zn(II), Cd(II), or Hg(II); and linear M(CN)2n- complexes of nd10 configuration where M=Ag(I), Au(I), or Hg(II). Except for Fe(CN)64-, the 13C resonance in all the cyano complexes is found at higher field than uncomplexed CN, and the range of chemical shifts spans 92.5 ppm. Chemical-shift differences are discussed in terms of changes in σ and π bonding of CN to the metal ion. Metal-13C spin coupling was observed for [FORMULA OMMITED] Relaxation times T1 and T2 are reported for enriched (45% 13C) samples of [FORMULA OMMITED] In addition T1 values for these complexes were measured at 10°C temperature intervals between 30 and 70°C. The mechanism of relaxation of the 13C nucleus in the cyano complexes is discussed with the data in most cases consistent with scalar coupling to 14N. © 1979, American Chemical Society. All rights reserved.
引用
收藏
页码:924 / 928
页数:5
相关论文
共 37 条
  • [1] POTASSIUM TETRACYANOPALLADATE(II)
    BIGELOW, JH
    [J]. INORGANIC SYNTHESES, 1946, 2 : 245 - 246
  • [2] POTASSIUM HEXACYANOCOBALTATE(III)
    BIGELOW, JH
    [J]. INORGANIC SYNTHESES, 1946, 2 : 225 - 227
  • [3] BODNER GM, 1974, INORG CHEM, V13, P1337
  • [4] C-13 NUCLEAR MAGNETIC-RESONANCE SPECTRA OF TUNGSTEN AND MOLYBDENUM CARBONYL DERIVATIVES
    BRATERMAN, PS
    MILNE, DW
    RANDALL, EW
    ROSENBERG, E
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1973, (10): : 1027 - 1031
  • [5] OXIDATIVE ADDITION-REACTIONS OF [PT(CN)4]2- - C-13 AND PT-195 NMR-STUDY
    BROWN, C
    HEATON, BT
    SABOUNCHEI, J
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1977, 142 (03) : 413 - 421
  • [6] MOLECULAR-ORBITAL THEORY OF ORGANOMETALLIC COMPOUNDS .14. CALCULATION OF C-13 NMR PARAMAGNETIC SHIELDING IN TRICARBONYLARENEMETALS
    BROWN, DA
    CHESTER, JP
    FITZPATRICK, NJ
    KING, IJ
    [J]. INORGANIC CHEMISTRY, 1977, 16 (10) : 2497 - 2500
  • [7] CHISHOLM MH, 1976, PROG INORG CHEM, V20, P299
  • [8] C-13 NUCLEAR MAGNETIC-RESONANCE STUDIES OF ORGANOPLATINUM(II) COMPLEXES CONTAINING SUBSTITUTED PYRIDINE LIGANDS
    COOPER, DG
    POWELL, J
    [J]. INORGANIC CHEMISTRY, 1977, 16 (01) : 142 - 148
  • [9] AMMONIUM HEXACHLOROOSMATE(IV)
    DWYER, FP
    HOGARTH, JW
    [J]. INORGANIC SYNTHESES, 1957, 5 : 206 - 207
  • [10] C-13 NMR OF 2 OCTAHEDRAL D6 TRANSITION-METAL CYANIDE COMPLEXES
    DYKES, D
    HUCKERBY, TN
    OLDHAM, C
    [J]. INORGANIC & NUCLEAR CHEMISTRY LETTERS, 1977, 13 (01): : 63 - 64