Hydrogen bonding in organometallic crystals .6. X-H---M hydrogen bonds and M---(H-X) pseudo-agostic bonds

被引：328

作者：

Braga, D ^{[1
]}

Grepioni, F ^{[1
]}

Tedesco, E ^{[1
]}

Biradha, K ^{[1
]}

Desiraju, GR ^{[1
]}

机构：

[1] UNIV HYDERABAD, SCH CHEM, HYDERABAD 500046, ANDHRA PRADESH, INDIA

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 09期

关键词：

D O I：

10.1021/om9608364

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The intermolecular interactions between X-H groups (X = C, N, and O) and metal atoms in crystalline organometallic complexes have been investigated. Molecular and crystal structures determined by neutron and/or X-ray diffraction data have been retrieved from the Cambridge Structural Database. The comparative analysis of intermolecular H ... M and X ... M distances as well as that of the X-H ... M angles allows a discrimination between the behavior of electrophilic and nucleophilic metal centers. Two novel types of interactions have been characterized: (i) the intermolecular multicenter hetero-acceptor (IMH) hydrogen bond formed when the X-H donor group interacts with M-X'(n) systems where M is an electron-rich metal and X' a metal-coordinated electronegative atom (X' = S, N, O, Cl); (ii) the intermolecular pseudo-agostic (IPA) interaction in which the X-H bond can donate electron density to electron deficient metal atoms M ...(H-X) as observed in intramolecular agostic interactions. Hydrogen bonding to metal centers in neutral complexes (X-H ... M) have been compared with charge assisted (X-H+... M-) hydrogen bonds involving electron-rich anionic complexes.

引用

页码：1846 / 1856

页数：11

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