103Rh NMR chemical shifts in organometallic complexes:: A combined experimental and density functional study

被引:42
作者
Orian, L
Bisello, A
Santi, S
Ceccon, A
Saielli, G
机构
[1] Univ Padua, Dipartimento Sci Chim, I-35131 Padua, Italy
[2] CNR, Ist Tecnol Membrance, Sez Padova, I-35131 Padua, Italy
关键词
bridging ligands; density functional calculations; NMR spectroscopy; rhodium;
D O I
10.1002/chem.200305671
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Experimental Rh-103 NMR chemical shifts of mono- and binuclear rhodium(I) complexes containing s- or as-hydroindacenide and indacenediide bridging ligands with different ancillary ligands (1,5-cyclooctadiene, ethylene, carbonyl) are presented. A protocol, based on density functional theory calculations, was established to determine Rh-103 NMR shielding constants in order to rationalise the effects of electronic and structural variations on the spectroscopic signal, and to gain insight into the efficiency of this computational method when applied to organometallic systems. Scalar and spin-orbit relativistic effects based on the ZORA (zeroth order regular approximation) level have been taken into account and discussed. A good agreement was found for model compounds over a wide range of chemical shifts of rhodium (approximate to 10000 ppm). This allowed us to discuss the experimental and calculated delta(Rh-103) in larger complexes and to relate it to their electronic structure.
引用
收藏
页码:4029 / 4040
页数:12
相关论文
共 104 条
[1]   ACTIVATION-ENERGIES FOR MOLECULAR TUMBLING AND CYCLOPENTADIENYL ROTATION IN [M(ETA-5-C5H5)(ETA-4-COD)] (M = RH OR IR, COD = CYCLO-OCTA-1,5-DIENE) AND THE X-RAY CRYSTAL-STRUCTURE OF AND BONDING IN [RH(ETA-5-C5H5)(ETA-4-COD)] [J].
ADAMS, H ;
BAILEY, NA ;
MANN, BE ;
TAYLOR, BF ;
WHITE, C ;
YAVARI, P .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1987, (08) :1947-1951
[2]  
AKERMARK B, 1991, ORGANOMETALLICS, V10, P733
[3]  
AKERMARK B, 1994, J AM CHEM SOC, V116, P3405, DOI 10.1021/ja00087a027
[4]   The Cambridge Structural Database: a quarter of a million crystal structures and rising [J].
Allen, FH .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 2002, 58 (3 PART 1) :380-388
[5]  
Amatore C, 1999, CHEM-EUR J, V5, P3357, DOI 10.1002/(SICI)1521-3765(19991105)5:11<3357::AID-CHEM3357>3.0.CO
[6]  
2-E
[7]   Structural effects in the reductive activation of (indenyl)RhL2 complexes: The reduction of [Rh(eta(5)-C9H7)(eta(4)-cod)] [J].
Amatore, C ;
Ceccon, A ;
Santi, S ;
Verpeaux, JN .
CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (02) :279-285
[8]  
ANDERSON SJ, 1978, J CHEM RES SYNOP, V286, P3601
[9]   Double perturbation theory: a powerful tool in computational coordination chemistry [J].
Autschbach, J ;
Ziegler, T .
COORDINATION CHEMISTRY REVIEWS, 2003, 238 :83-126
[10]  
AUTSCHBACH J, 2002, RELATIVISTIC COMPUUN, V9