When VSEPR Fails: Experimental and Theoretical Investigations of the Behavior of Alkaline-Earth-Metal Acetylides

The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline‐earth‐metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication...

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Bibliographic Details
Published in:	Chemistry : a European journal Vol. 15; no. 44; pp. 11842 - 11852
Main Authors:	Guino-o, Marites A., Alexander, Jacob S., McKee, Michael L., Hope, Håkon, Englich, Ulrich B., Ruhlandt-Senge, Karin
Format:	Journal Article
Language:	English
Published:	Weinheim WILEY-VCH Verlag 09-11-2009 WILEY‐VCH Verlag
Subjects:	Acetylene - chemistry acetylides alkaline earth metals Metals, Alkaline Earth - chemistry Models, Chemical Models, Molecular Molecular Conformation Organometallic Compounds - chemistry secondary interactions Spectrophotometry, Infrared structure elucidation structure-determining factors
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Summary:	The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline‐earth‐metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl‐substituted alkaline‐earth‐metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline‐earth‐metal chemistry. Bent or not bent? The experimental and theoretical analysis of factors responsible for the unusual geometry of heavier alkaline‐earth‐metal derivatives (see picture) provide unique insight into structure‐determining factors in heavy s‐block chemistry.
Bibliography:	National Science Foundation - No. DMR 0225180 Syracuse University Macromolecular Diffraction at CHESS (MacCHESS) - No. RR-01646 National Science Foundation - No. CHE-0505863; No. 0753807 istex:3361776FD099C3B5414EB9F9C92CA98EDD90DA6A ark:/67375/WNG-NPJBNF2C-0 ArticleID:CHEM200901538 NSF - No. CHE-95-27898 National Institutes of Health W.M. Keck Foundation ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 Current address: Department of Chemistry, Barnard College, 3009 Broadway, New York, NY 10027 (USA)
ISSN:	0947-6539 1521-3765
DOI:	10.1002/chem.200901538