STRUCTURE AND ELECTRONIC STATE OF MOLYBDENUM SUBCARBONYL SPECIES ENCAGED IN ZEOLITE

被引:43
作者
OKAMOTO, Y [1 ]
IMANAKA, T [1 ]
ASAKURA, K [1 ]
IWASAWA, Y [1 ]
机构
[1] UNIV TOKYO,FAC SCI,DEPT CHEM,BUNKYO KU,TOKYO 113,JAPAN
关键词
D O I
10.1021/j100162a049
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The structure and electronic state of molybdenum subcarbonyl species anchored in alkali-metal cation exchanged zeolites were elucidated by means of EXAFS, IR, and XPS analyses. The subcarbonyl species were produced at 373 K by evacuating Mo(CO)6 entrapped in the zeolite. The structure of the Mo-subcarbonyl species was found to be monomeric Mo(CO)3(OZ)3 with a fac configuration (OZ: zeolite framework oxygen). The Mo-C bond distance is very short (0.186-0.189 nm), suggesting strong d --> pi* back donations from the Mo atom to the CO ligands. The electron density of Mo in Mo(CO)3(OZ)3 increases with increasing basic strength of OZ in the order HY approximately LiY < NaY approximately CsY.
引用
收藏
页码:3700 / 3705
页数:6
相关论文
共 44 条
[11]   SYNTHESES, STRUCTURES, AND MOLECULAR-ORBITAL ANALYSIS OF HYDRIDOTRIS(PYRAZOLYL)BORATE (TP) MOLYBDENUM CARBONYLS - PARAMAGNETIC TPMO(CO)3 AND TRIPLY BONDED TP2MO2(CO)4 (MO = MO) [J].
CURTIS, MD ;
SHIU, KB ;
BUTLER, WM ;
HUFFMAN, JC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (12) :3335-3343
[12]  
GALLEZOT P, 1977, ACS SYM SER, P144
[13]  
Gates B.C., 1986, METAL CLUSTERS CATAL
[14]   X-RAY PHOTOELECTRON-SPECTROSCOPY OF INORGANIC AND ORGANOMETALLIC COMPOUNDS OF MOLYBDENUM [J].
GRIM, SO ;
MATIENZO, LJ .
INORGANIC CHEMISTRY, 1975, 14 (05) :1014-1018
[15]   MOLECULAR-STRUCTURE OF THE MO-MO TRIPLE-BONDED PENTAMETHYLCYCLOPENTADIENYLMOLYBDENUM DIMER, MO2(E-TA-5-C5ME5)2(CO)4, AND ITS GEOMETRICAL RELATIONSHIP WITH THE NON-METHYLATED CYCLOPENTADIENYL ANALOG (MO=MO) AND CORRESPONDING CHROMIUM DIMERS (CR=CR) [J].
HUANG, JS ;
DAHL, LF .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1983, 243 (01) :57-68
[16]   CHEMICAL DESIGN SURFACES FOR ACTIVE SOLID CATALYSTS [J].
IWASAWA, Y .
ADVANCES IN CATALYSIS, 1987, 35 :187-264
[17]   A REVERSIBLE MO-2-O-2 COMPLEX CHEMICALLY FIXED ON AN SIO2 SURFACE [J].
IWASAWA, Y ;
YAMAGISHI, M ;
OGASAWA, S .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1982, (04) :246-248
[18]  
IWASAWA Y, 1986, TAILORED METAL CATAL, P1
[19]  
Iwasawa Y., 1986, TAILORED METAL CATAL
[20]   INFRARED SPECTROSCOPIC STUDIES ON THE PHOTOCATALYTIC HYDROGENATION OF NORBORNADIENE BY GROUP-6 METAL-CARBONYLS .1. THE ROLE OF H-2 AND THE CHARACTERIZATION OF NONCLASSICAL DIHYDROGEN COMPLEXES, (ETA-4-NORBORNADIENE)M(CO)3(ETA-2-H2) [J].
JACKSON, SA ;
HODGES, PM ;
POLIAKOFF, M ;
TURNER, JJ ;
GREVELS, FW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (03) :1221-1233