Structure and fluxional behavior of (eta(4)-butadiene)Fe(CO)(2)L (L=CO, PH3, PMe(3)) complexes. A density functional study

被引：16

作者：

GonzalezBlanco, O ^{[1
]}

Branchadell, V ^{[1
]}

机构：

[1] UNIV AUTONOMA BARCELONA,DEPT QUIM,BELLATERRA 08193,SPAIN

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 03期

关键词：

D O I：

10.1021/om960896+

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The structure and fluxional behavior of (eta(4)-butadiene)Fe(CO)(2)L (L = CO, PH3, PMe(3)) complexes have been studied using density functional methods. For (butadiene)Fe(CO)(3), the geometry obtained is in excellent agreement with the gas-phase experimental data. The calculation of the harmonic vibrational frequencies has permitted the reassignment of several frequencies observed in the IR and Raman spectra. The computed Fe-butadiene binding energy is in all cases about 52 kcal mol(-1), in excellent agreement with the experimental data corresponding to the (butadiene)Fe(CO)(3) complex. The nature of the bonding has been analyzed in terms of steric and electronic interactions. The butadiene-Fe rotational barriers have been computed, and the origin of the barrier has been discussed.

引用

页码：475 / 481

页数：7

共 49 条

[21] CONTRIBUTION TO COHESIVE ENERGY OF SIMPLE METALS - SPIN-DEPENDENT EFFECT [J].

GUNNARSSON, O ;

LUNDQVIST, BI ;

WILKINS, JW .

PHYSICAL REVIEW B, 1974, 10 (04) :1319-1327

[22] ABINITIO STUDIES OF POLYENES .1. 1,3-BUTADIENE [J].

GUO, H ;

KARPLUS, M .

JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (05) :3679-3699

[23] THEORETICAL ASPECTS OF COORDINATION OF MOLECULES TO TRANSITION-METAL CENTERS [J].

HOFFMANN, R ;

ALBRIGHT, TA ;

THORN, DL .

PURE AND APPLIED CHEMISTRY, 1978, 50 (01) :1-9

[24] COMPARISON OF THE MOLECULAR-STRUCTURES AND SOLUTION STEREODYNAMICS OF (DIENE)FE(CO)2L COMPLEXES (L=CO, PPH3, P(OME)3, PME3, NME3, PYRIDINE, CNME) [J].

HOWELL, JAS ;

BELL, AG ;

CUNNINGHAM, D ;

MCARDLE, P ;

ALBRIGHT, TA ;

GOLDSCHMIDT, Z ;

GOTTLIEB, HE ;

HEZRONILANGERMAN, D .

ORGANOMETALLICS, 1993, 12 (07) :2541-2548

[25] SYNTHESIS, STRUCTURE, REACTIVITY, AND DIASTEREOISOMER SEPARATION OF (TROPONE)FE(CO)2L COMPLEXES (L = PPH3, (+)-NEOMENTHYLDIPHENYLPHOSPHINE) [J].

HOWELL, JAS ;

SQUIBB, AD ;

GOLDSCHMIDT, Z ;

GOTTLIEB, HE ;

ALMADHOUN, A ;

GOLDBERG, I .

ORGANOMETALLICS, 1990, 9 (01) :80-91

[26]

KRIJN K, 1984, FIT FUNCTIONS HFS ME

[27] FLUXIONAL BEHAVIOR OF (DIENE)IRON TRICARBONYL TYPE COMPLEXES [J].

KRUCZYNSKI, L ;

TAKATS, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (03) :932-934

[28] INTRAMOLECULAR REARRANGEMENT IN (ETA-DIENE)TRICARBONYLIRON AND (ETA-DIENE)TRICARBONYLRUTHENIUM COMPOUNDS - C-13 NUCLEAR MAGNETIC-RESONANCE STUDY [J].

KRUCZYNSKI, L ;

TAKATS, J .

INORGANIC CHEMISTRY, 1976, 15 (12) :3140-3147

[29] MICROWAVE MEASUREMENTS OF THE ROTATIONAL SPECTRUM OF BUTADIENE IRON TRICARBONYL [J].

KUKOLICH, SG ;

ROEHRIG, MA ;

HENDERSON, GL ;

WALLACE, DW ;

CHEN, QQ .

JOURNAL OF CHEMICAL PHYSICS, 1992, 97 (02) :829-831

[30] MICROWAVE MEASUREMENTS OF THE ROTATIONAL SPECTRUM AND STRUCTURE OF (BUTADIENE)IRON TRICARBONYL [J].

KUKOLICH, SG ;

ROEHRIG, MA ;

WALLACE, DW ;

HENDERSON, GL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (05) :2021-2027

← 1 2 3 4 5 →