INNER-SHELL EXCITATION OF ETA-5-C5H5CO(CO)2 AND RELATED-COMPOUNDS STUDIED BY GAS-PHASE ELECTRON-ENERGY LOSS SPECTROSCOPY

被引:25
作者
RUHL, E [1 ]
WEN, AT [1 ]
HITCHCOCK, AP [1 ]
机构
[1] FREE UNIV BERLIN,INST PHYS CHEM,W-1000 BERLIN 33,GERMANY
基金
加拿大自然科学与工程研究理事会;
关键词
D O I
10.1016/0368-2048(91)85020-T
中图分类号
O433 [光谱学];
学科分类号
0703 ; 070302 ;
摘要
Oscillator strengths for carbon 1s, oxygen 1s and cobalt 2p excitation of CpCo(CO)2 (Cp = eta-5-cyclopentadienyl) have been derived from inner-shell electron energy loss spectra recorded under scattering conditions dominated by electric dipole transitions. The spectral features have been assigned on the basis of comparison with the spectra of the free ligands and with previously studied gas phase organocobalt complexes, Co2 (CO)8 and Co (Cp)2, along with extended Huckel molecular orbital calculations. Comparisons of the core spectra of free and complexed ligands provide information on metal-ligand bonding. A simulation of the C1s spectrum of CPCO(CO)2, a weighted sum of the Co2 (CO)8 and Co (Cp)2 spectra, duplicates all features of the experimental spectrum, implying that the virtual orbitals of the ligands (as sampled by core excitation) are relatively independent of those of the other ligands. Quantitative deviations from this "building block" model reveal that the virtual MOs associated with Cp are more influenced by ligand-ligand interaction than those associated with the carbonyl ligand. These results provide a first view of the extent to which core excitation spectroscopy will be useful in studying the electronic structure of complex organometallic compounds with mixtures of ligands.
引用
收藏
页码:137 / 164
页数:28
相关论文
共 62 条
[1]   CONFORMATIONAL PREFERENCES AND ROTATIONAL BARRIERS IN POLYENE-ML3 TRANSITION-METAL COMPLEXES [J].
ALBRIGHT, TA ;
HOFMANN, P ;
HOFFMANN, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (23) :7546-7557
[2]   EXCITATION AND IONIZATION AT SURFACES - CO ON METALS [J].
AVOURIS, P ;
BAGUS, PS ;
ROSSI, AR .
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY B, 1985, 3 (05) :1484-1489
[3]   HARTREE-FOCK-SLATER CALCULATIONS ON CHARGE-DISTRIBUTION AND LIGAND 1S BINDING-ENERGY SHIFTS IN CARBONYL-COMPLEXES [J].
BAERENDS, EJ ;
ROS, P .
JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA, 1975, 7 (01) :69-74
[4]   THE NATURE OF THE METAL CO INTERACTION AND BONDING [J].
BAGUS, PS ;
NELIN, CJ ;
BAUSCHLICHER, CW .
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A-VACUUM SURFACES AND FILMS, 1984, 2 (02) :905-909
[5]   GAS-PHASE ELECTRON-DIFFRACTION STUDY OF THE MOLECULAR-STRUCTURE OF CYCLOPENTADIENYL COBALT DICARBONYL, C5H5CO(CO)2 [J].
BEAGLEY, B ;
PARROTT, CT ;
ULBRECHT, V ;
YOUNG, GG .
JOURNAL OF MOLECULAR STRUCTURE, 1979, 52 (01) :47-52
[6]   THEORETICAL INVESTIGATION OF HYDROFORMYLATION REACTIONS .1. STRUCTURES AND REACTIVITIES OF COBALT CARBONYLS AND HYDROCARBONYLS [J].
BELLAGAMBA, V ;
ERCOLI, R ;
GAMBA, A ;
SUFFRITTI, GB .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1980, 190 (04) :381-392
[7]   CO-59 NMR-SPECTROSCOPY OF ORGANOCOBALT(I) AND ORGANOCOBALT(III) COMPOUNDS AND ITS RELATION TO CHEMICAL-PROPERTIES OF THE COMPLEXES [J].
BENN, R ;
CIBURA, K ;
HOFMANN, P ;
JONAS, K ;
RUFINSKA, A .
ORGANOMETALLICS, 1985, 4 (12) :2214-2221
[8]   EXPLANATION OF REACTIVITIES OF PI-C3H5CO(CO)3 AND PI-C5H5CO(CO)2 [J].
BROWN, DA ;
CLARKE, HL ;
FITZPATR.NJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1973, 47 (01) :C11-C12
[9]   STRUCTURAL-ANALYSIS OF (PENTAMETHYLCYCLOPENTADIENYL)COBALT(I) DICARBONYL - EVIDENCE FOR AN ELECTRONICALLY INDUCED DISTORTION OF THE CYCLOPENTADIENYL RING DUE TO ITS INTERACTION WITH A PLANAR CO(CO)2 FRAGMENT [J].
BYERS, LR ;
DAHL, LF .
INORGANIC CHEMISTRY, 1980, 19 (02) :277-284
[10]   STUDY OF THE BONDING IN TRANSITION-METAL CARBONYL HYDRIDES [J].
CHEN, HW ;
JOLLY, WL ;
KOPF, J ;
LEE, TH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (10) :2607-2610