Cp2ZrCH(SiMe3)CCCH(SiMe3):: A five-membered 1-zirconacyclopent-3-yne?

被引：43

作者：

Lam, KC

Lin, ZY

机构：

[1] Hong Kong Univ Sci & Technol, Dept Chem, Inst Mol Technol Drug Discovery & Synth, Kowloon, Hong Kong, Peoples R China

[2] Hong Kong Univ Sci & Technol, Open Lab Chirotechnol, Inst Mol Technol Drug Discovery & Synth, Kowloon, Hong Kong, Peoples R China

来源：

ORGANOMETALLICS | 2003年 / 22卷 / 17期

关键词：

D O I：

10.1021/om0302950

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional theory calculations at the B3LYP level were performed to study the electronic structure of a recently synthesized zirconocene complex, Cp2ZrCHRCCCHR (R = SiMe3). Through detailed bonding analyses and stability studies, we conclude that the originally proposed metallacyclopentyne form cannot adequately describe the complex. Instead, a resonance hybrid between a cumulene complex form and a metallacyclopentyne Lewis structure is required to account for the structure and stability of the complex.

引用

页码：3466 / 3470

页数：5

共 36 条

[1]

Albright T.A., 1985, ORBITAL INTERACTIONS

[2] SMALL-RING CYCLIC CUMULENES - THE STRUCTURE AND ENERGETICS OF CYCLIC BUTATRIENES AND THE SYNTHESIS OF 1,2,3-CYCLONONATRIENE [J].

ANGUS, RO ;

JOHNSON, RP .

JOURNAL OF ORGANIC CHEMISTRY, 1984, 49 (16) :2880-2883

[3] ATOMS IN MOLECULES [J].

BADER, RFW .

ACCOUNTS OF CHEMICAL RESEARCH, 1985, 18 (01) :9-15

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

BECKE, AD .

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

[5] COMPACT CONTRACTED BASIS-SETS FOR 3RD-ROW ATOMS - GA-KR [J].

BINNING, RC ;

CURTISS, LA .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1990, 11 (10) :1206-1216

[6] REACTIVITY AND STRUCTURE OF (S-CIS-1,3-DIENE)ZIRCONOCENE COMPLEXES [J].

ERKER, G ;

ENGEL, K ;

KRUGER, C ;

CHIANG, AP .

CHEMISCHE BERICHTE-RECUEIL, 1982, 115 (10) :3311-3323

[7] Competing metal-pi-acetylene and metal-sigma-(H-Si) interactions in the complex Ti(eta(5)-C5H5)(2)(eta(2)-trans-RC CSiHR(2)) [J].

Fan, MF ;

Lin, ZY .

ORGANOMETALLICS, 1997, 16 (03) :494-496

[8]

Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V16, P01

[9] STRUCTURE OF THE HIGHLY CROWDED ALKYNE DI[TRIS(TRIMETHYLSILYL)METHYL]ACETYLENE AND THE OCTASILANE HEXAKIS(TRIMETHYLSILYL)DISILANE [J].

FRONCZEK, FR ;

LICKISS, PD .

ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1993, 49 :331-333

[10] THE ISOMERS OF SILACYCLOPROPANE [J].

GORDON, MS .

CHEMICAL PHYSICS LETTERS, 1980, 76 (01) :163-168

← 1 2 3 4 →