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

[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] ROTATIONAL BARRIERS AND CONFORMATIONS IN TRANSITION-METAL COMPLEXES [J].

ALBRIGHT, TA .

ACCOUNTS OF CHEMICAL RESEARCH, 1982, 15 (05) :149-155

[3] Self-consistent molecular Hartree-Fock-Slater calculations - I. The computational procedure [J].

Baerends, E. J. ;

Ellis, D. E. ;

Ros, P. .

CHEMICAL PHYSICS, 1973, 2 (01) :41-51

[4] AN ABINITIO STUDY OF FE(CO)1, FE(CO)5, AND CR(CO)6 [J].

BARNES, LA ;

ROSI, M ;

BAUSCHLICHER, CW .

JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (03) :2031-2039

[5] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[6] INTRAMOLECULAR CARBONYL GROUP SITE EXCHANGE IN SYMMETRICALLY SUBSTITUTED (ETA-1,3-DIENE)TRICARBONYLIRON COMPLEXES [J].

BISCHOFBERGER, P ;

HANSEN, HJ .

HELVETICA CHIMICA ACTA, 1982, 65 (03) :721-725

[7] CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].

BOYS, SF ;

BERNARDI, F .

MOLECULAR PHYSICS, 1970, 19 (04) :553-&

[8] ROTATIONAL BARRIERS IN TRIMETHYLENEMETHANE FE(CO)2L COMPLEXES - A DENSITY-FUNCTIONAL STUDY [J].

BRANCHADELL, V ;

DENG, LQ ;

ZEIGLER, T .

ORGANOMETALLICS, 1994, 13 (08) :3115-3119

[9] ENTHALPIES OF THERMAL-DECOMPOSITION OF IRON-OLEFIN COMPLEXES, AND STRENGTHS OF IRON-OLEFIN BONDS [J].

BROWN, DLS ;

CONNOR, JA ;

LEUNG, ML ;

PAZANDRADE, MI ;

SKINNER, HA .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1976, 110 (01) :79-89

[10] MOLECULAR-ORBITAL CALCULATIONS ON MODEL FE(CO)2L(ETA-4-ENONE) COMPLEXES WITH L = CO, PH3, AND P(OH)3 - ELECTRONIC AND STERIC EFFECTS IN FE(CO)2L(ETA-4-BENZYLIDENEACETONE) [J].

CALHORDA, MJ ;

VICHI, EJS .

ORGANOMETALLICS, 1990, 9 (04) :1060-1067

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