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Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
The oxidation number of rhodium, x, must therefore be +3. Practice Exercise What is the charge of the complex formed by a platinum(II) metal ion surrounded by two ammonia molecules and two bromide ions? Answer: zero
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
The charge on the ion is 1+, [Cr(H2O)4Cl2]+. Practice Exercise Write the formula for the complex described in the Practice Exercise accompanying Sample Exercise 24.2. Answer: [Pt(NH3)2Br2]
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
where the dashed vertical line represents a mirror. Notice that the mirror image of the trans isomer is identical to the original. Consequently trans-[Co(en)2Cl2 ]+ does not exhibit optical isomerism. The mirror image of the cis isomer of [Co(en)2Cl2]+, however, cannot be superimposed on the original
Thus, the two cis structures are optical isomers (enantiomers): cis-[Co(en)2Cl2 ]+ is a chiral complex.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Sample Exercise 24.9 Predicting the Number of Unpaired Electrons in an Octahedral Complex
Predict the number of unpaired electrons in six-coordinate high-spin and low-spin complexes of Fe3+ . Solution Analyze: We must determine how many unpaired electrons there are in the highspin and low-spin complexes of the metal ion Fe3+. Plan: We need to consider how the electrons populate d orbitals for Fe3+ when the metal is in an octahedral complex. There are two possibilities: one giving a high-spin complex and the other giving a low-spin complex. The electron configuration of Fe3+ gives us the number of d electrons. We then determine how these electrons populate the t2 set and e set of d orbitals. In the high-spin case, the energy difference between the t2 and e orbitals is small, and the complex has the maximum number of unpaired electrons. In the low-spin case, the energy difference between the t2 and e orbitals is large, causing the t2 orbitals to be filled before any electrons occupy the e orbitals. Solve: Fe3+ is a d5 ion. In a high-spin complex, all five of these electrons are unpaired, with three in the t2 orbitals and two in the e orbitals. In a low-spin complex, all five electrons reside in the t2 set of d orbitals, so there is one unpaired electron:
Practice Exercise For which d electron configurations in octahedral complexes is it possible to distinguish between high-spin and low-spin arrangements? Answer: d4, d5, d6, d7
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Comment: Notice that the tetrahedral complex is paramagnetic with two unpaired electrons, whereas the square-planar complex is diamagnetic. Nickel(II) forms octahedral complexes more frequently than squareplanar ones, whereas heavier d8 metals tend to favor square planar coordination.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
(d) The ortho-phenanthroline ligand is bidentate, like the oxalate ligand, so they both exhibit the chelate effect. Thus, we can conclude that ortho-phenanthroline is a stronger Lewis base toward Co2+ than oxalate. This conclusion is consistent with what we learned about bases in Section 16.7, namely that nitrogen bases are generally stronger than oxygen bases. (Recall, for example, that NH3 is a stronger base than H2O.)
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward
Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.
Because Kf is so large, we can assume that essentially all of the Co2+ is converted to the oxalato complex. Under that assumption, the final concentration of [Co(Ox)3]3 is 0.0010 M and that of oxalate ion is [Ox2] = (0.040) 3(0.0010) = 0.037 M (three Ox2 ions react with each Co2+ ion). We then have
Solving for x, we obtain 4 10-9 M. From this, we can see that the oxalate has complexed all but a tiny fraction of the Co2+ present in solution.
Chemistry: The Central Science, Eleventh Edition By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy With contributions from Patrick Woodward Copyright 2009 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved.