Structure and Bonding Energy Analysis of Cationic Metal-Ylyne Complexes of Molybdenum and Tungsten, [(MeCN)(PMe3)4MEMes]+ (M = Mo, W; E = Si, Ge, Sn, Pb): A Theoretical Study

被引：12

作者：

Pandey, Krishna K. ^{[1
]}

Patidar, Pankaj ^{[1
]}

Power, Philip P. ^{[2
]}

机构：

[1] Devi Ahilya Univ Indore, Sch Chem Sci, Indore 452017, Madhya Pradesh, India

[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

INORGANIC CHEMISTRY | 2011年 / 50卷 / 15期

关键词：

ORDER REGULAR APPROXIMATION; TRANSITION-METAL; GERMYLYNE COMPLEXES; TRIPLE BONDS; DECOMPOSITION ANALYSIS; GERMYLIDYNE COMPLEXES; TP-ASTERISK; CP-ASTERISK; MAIN-GROUP; CL;

D O I：

10.1021/ic2005908

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The molecular and electronic structures and bonding analysis of terminal cationic metal-ylyne complexes (MeCN)(PMe3)(4)M equivalent to EMes](+) (M = Mo, W; E = Si, Ge, Sn, Pb.) were investigated using DFT/BP86/TZ2P/ZORA level of theory. The calculated geometrical parameters for the model complexes are in good agreement with the reported experimental values. The M-E sigma-bonding orbitals are slightly polarized toward E except in the complex [(MeCN)(PMe3)(4)W(SnMes)](+), where the M-E sigma-bonding orbital is slightly polarized toward the W atom. The M-E pi-bonding orbitals are highly polarized toward the metal atom. In all complexes, the pi-bonding contribution to the total M equivalent to EMes bond is greater than that of the sigma-bonding contribution and increases upon going from M = Mo to W. The values of orbital interaction Delta E-orb are significantly larger in all studied complexes I-VIII than the electrostatic interaction AE(elstat). The absolute values of the interaction energy, as well as the bond dissociation energy, decrease in the order Si > Ge > Sn > Pb, and the tungsten complexes have stronger bonding than the molybdenum complexes.

引用

页码：7080 / 7089

页数：10

共 65 条

[1]

[Anonymous], TRANSITION METAL CAR

[2] 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

[3]

Baerends E. J., ADF 2009 01 SCI COMP

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

BECKE, AD .

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

[5] REGULAR 2-COMPONENT PAULI-LIKE EFFECTIVE-HAMILTONIANS IN DIRAC THEORY [J].

CHANG, C ;

PELISSIER, M ;

DURAND, P .

PHYSICA SCRIPTA, 1986, 34 (05) :394-404

[6] Poly(1,6-heptadiyne)-based materials by metathesis polymerization [J].

Choi, SK ;

Gal, YS ;

Jin, SH ;

Kim, HK .

CHEMICAL REVIEWS, 2000, 100 (04) :1645-1681

[7] Synthesis of a Thiocarbamoyl Alkylidyne Complex and Caveats Associated with the Use of [Mo(CLi)(CO)2(Tp*)] (Tp* = Hydrotris(3,5-dimethylpyrazol-1-yl)borate) [J].

Colebatch, Annie L. ;

Hill, Anthony F. ;

Shang, Rong ;

Willis, Anthony C. .

ORGANOMETALLICS, 2010, 29 (23) :6482-6487

[8] Group 14 Substituted Carbyne Complexes-An Almost Complete Set: [Mo(CAPh3)(CO)2(Tp*)] (Tp* = Hydrotris(dimethylpyrazolyl) borate; A = Si, Ge, Sn, Pb but A ≠ C) [J].

Cordiner, Richard L. ;

Hill, Anthony F. ;

Shang, Rong ;

Willis, Anthony C. .

ORGANOMETALLICS, 2011, 30 (01) :139-144

[9] Phosphino and Phosphonito Carbyne Complexes: [MO(CX)(CO)2{HB(pzMe2)3}] (X = PPh2, P(=O)(OEt)2; pz = Pyrazol-1-yl) [J].

Cordiner, Richard L. ;

Gugger, Paul A. ;

Hill, Anthony F. ;

Willis, Anthony C. .

ORGANOMETALLICS, 2009, 28 (23) :6632-6635

[10]

Cotton A. F., 1999, ADV INORG CHEM, V6th

← 1 2 3 4 5 6 7 →