Skip to main content Accessibility help
×
Hostname: page-component-78c5997874-8bhkd Total loading time: 0 Render date: 2024-11-09T13:07:42.093Z Has data issue: false hasContentIssue false

Problem Answers

Published online by Cambridge University Press:  19 February 2010

Thomas Fehlner
Affiliation:
University of Notre Dame, Indiana
Jean-Francois Halet
Affiliation:
Université de Rennes I, France
Jean-Yves Saillard
Affiliation:
Université de Rennes I, France
Get access

Summary

1. (a) Approach: Cr possesses six valence electrons, thus ligands must be chosen to supply 12 more to satisfy the 18-electron rule, e.g., six CO ligands; Mn possesses seven valence electrons, thus ligands need to supply 11, e.g., 5 CO + 1 H. (b) This problem requires recognition of the types of bonds in the molecule and which ones, if any, are unusual. The answer to part (a) suggests the Cr–CO bonds can be adequately described as two-center donor–acceptor bonds. The Cr–H–Cr with a two-coordinate H atom is clearly the unusual situation; hence, a fragmentation into two Cr(CO)5 fragments and an Hanion is appropriate. A Cr(CO)5 fragment is a 16-electron species with an empty orbital available to accept an electron pair. The H anion possesses one filled orbital; hence, the three orbitals (two from the metal fragments and one from H) can be used to form one bonding, one non-bonding and one antibonding three-center orbital with the bonding combination containing the two available electrons.

2. S contributes four AOs and the six H atoms contribute six AOs for a total of ten leading to ten MOs. The central atom has functions of symmetry a1g (3s) and t1u (3p), whereas the six ligand functions have symmetry-adapted combinations of a1g (3s) and t1u, and eg just like an octahedral transition-metal complex. As shown below, interaction between the central atom and the ligands generates four bonding MOs plus their antibonding partners and two non-bonding orbitals having ligand character only for atotal of ten MOs.

Type
Chapter
Information
Molecular Clusters
A Bridge to Solid-State Chemistry
, pp. 349 - 368
Publisher: Cambridge University Press
Print publication year: 2007

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Save book to Kindle

To save this book to your Kindle, first ensure [email protected] is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about saving to your Kindle.

Note you can select to save to either the @free.kindle.com or @kindle.com variations. ‘@free.kindle.com’ emails are free but can only be saved to your device when it is connected to wi-fi. ‘@kindle.com’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

Find out more about the Kindle Personal Document Service.

Available formats
×

Save book to Dropbox

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Dropbox.

Available formats
×

Save book to Google Drive

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Google Drive.

Available formats
×