Assignment 30 STRUCTURE OF MOLECULES AND MULTI-ATOM IONS - Part II In Assignment 10, you predicted the three-dimensional shapes of molecules

and multi-atom ions based on electron dot diagrams, which explicitly depicted the number of electron pairs surrounding a central atom. In this Assignment, only the chemical formula will be given. From this formula, you will develop an electron dot diagram, which will allow you to predict the electron pair shape and molecular shape as in Assignment 10. The following step-by-step procedure explains how to deduce molecular shape from a given formula. As an example, the right hand column shows how each step would be used to determine the shape of permanganate ion, MnO4. Deducing the shape of single center molecules and multi-atom ions from a given formula. 1. From the given formula, you should identify a central atom which is surrounded by ligands. 2. To construct the electron dot structure, an electron counting mechanism is employed:
Determine the total number of electrons in the formula by adding the valence shell electrons for each neutral atom (the valence shell electrons are found from the electron dot diagram for the neutral atom). Adjust this total by adding or subtracting electrons to account for the charge on the formula. From this pool of electrons, each ligand takes 8 electrons to complete an octet (except for H, which takes only 2 electrons). Any electrons remaining from the pool constitute lone pairs on the central atom. Note that the central atom in a hypervalent compound may have more than 8 electrons ( see example 5 ). If the pool does not contain enough electrons to provide an octet on each ligand, then additional d or f inner shell electrons (not shown on electron dot diagrams) must be provided from the central atom.

(MnO4 contains the center Mn atom and four surrounding O atoms.)

(MnO4 contains one Mn atom, four surrounding O atoms, and has an overall 1 charge, giving a total electron pool of 2e + 4x6e + 1e = 27e.) (To octet each oxygen ligand atom requires 4 x 8e = 32e. Subtracting the 32 required electrons from the available pool of 27e leaves a deficiency of 5 electrons (27e 32e = 5e). Since there are no leftover electrons, there are no lone pairs on the Mn atom.) (For MnO4 the five additional electrons required to completely octet the ligand atoms must come from the 3d orbitals of Mn.)

3. Next draw an electron dot diagram for the formula by taking the central atom -- including any lone pairs -- and surrounding it with the correct number of ligands (each having an octet). Note: the lone pairs on the central atom are NEVER used for bonding with the ligands -- they remain completely with the central atom. 4. Once you have the electron dot diagram, analyze it for electron pair shape and for molecular (or complex ion) shape as described in Assignment 10.

tetrahedral

tetrahedral
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5. If your predicted electron dot diagram shows the central atom with less than four electron pairs surrounding it, recall the treatment of this situation using -bonding and/or resonance ideas from Assignment 10. For second row atoms -- especially C, N and O -- formation of -bonds is a frequent and important phenomenon for completing octet structures for the central atom. For larger atoms there is only a limited or partial -bonding contribution. EXAMPLES: 1) NH4+ ammonium ion Center atom? N Total electrons?

Ligand atoms? 4 H 1xN = 1x 5e = 5e 4xH = 4 x 1e = 4e Ion charge (one less e) = -1e Total pool = 8e

Charge? +1 (one electron gone)

To "octet" ligands?

4 x (H) = 4 x 2e = 8e (Of the total pool of 8e, 8e are used to "octet" ligands)

Electrons on central atom? N = 8e - 8e = no e Electron dot diagram? (N, with no lone pairs, and 4 "octeted" ligands)

Electron pair shape? Tetrahedral 2)

Molecular shape? Tetrahedral

BrF3

bromine trifluoride Ligand atoms? 3F Charge? zero 1 x Br = 1 x 7e = 7e 3 x F = 3 x 7e = 21e Ion charge Total pool = no e = 28e (Of the total pool of 28e, 24e are used to octet ligands)

Center atom? Br Total electrons?

To octet ligands? Electrons on central atom? Electron dot diagram?

3x(F) = 3 x 8e = 24e

Br = 28e - 24e = 4e, or 2 lone pairs

Electron Pair Shape? trigonal bipyramidal

Molecular shape? T-shaped (note position of lone pairs)

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HYBRID ORBITALS

In lecture you have learned about atomic orbitals (AOs)the regions of space surrounding an atoms nucleus that house that atoms electrons. A carbon atom has four available atomic orbitals--one 2s AO, and three 2p AOs (2px, 2py, 2pz) to house its four valence electrons. Take a look at the shapes and orientations of carbons valence AOs shown at right. If a bond is formed by the overlap of atomic orbitals, then to form a molecule of methane, CH4, each of these C atomic orbitals must overlap with an H 1s atomic orbital to form four C-H bonds. The problem is that such an overlap would result in two different types of C-H bond (one C(2s) - H(1s) overlap and three C(2p) H(1s) overlaps) with the three C(2p) H(1s) overlaps producing C-H bonds mutually perpendicular to each other. Neither of these attributes is observed experimentally! Recall that for a CH4 molecule, the procedures of this Assignment would predict a tetrahedral geometry in which four identical C-H bonds are spaced as far apart from each other as possible (109.5 bond angles). We cant explain CH4s known geometry using our localized electron model of bonding unless we allow for the possibility that the central carbon atom is capable of rearranging its individual atomic orbitals as needed to attain the most stable (lowest energy) condition for the molecule. Although the atomic orbitals in an isolated C atom are not the best for bonding, the four C atomic orbitals can be combined and rearranged (hybridized) to form four new hybrid atomic orbitals (or hybrid orbitals, HOs) which do possess the appropriate orientation for bonding (Fig. 1). In this case, the four orbitals produced are named sp3 hybrid atomic orbitals because they result from mixing one s-type AO and three p-type AOs of the C atom. The number of AOs used to create hybrid atomic orbitals must equal the number of HOs produced! Thus, there are four sp3 hybrid orbitals. This phenomenon is called orbital conservation. Note that in the CH4 example, no -bonds are expected in the molecule because the central atom has a complete octet. The expectation of no -bonding also makes sense from an atomic orbital standpoint if all of carbons p-AOs are involved in creating the bonding HOs, there are no empty p-atomic orbitals left to participate in -bonding.

Figure 1

The idea that individual atoms can rearrange their atomic orbitals as needed to achieve the minimum energy for the molecule is an assumption of this model of bonding. The five common orbital hybridization names and the corresponding electron pair shapes are listed in the following table:

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Number of electron pairs (-bonds and lone) 1 2 3 4 5 6

Electron pair shape (Not appropriate) Linear Trigonal coplanar Tetrahedral Trigonal bipyramidal Octahedral

Orbital Hybridization (Not appropriate) sp sp2 sp3 sp3d sp3d2

NOTE: Each orbital hybridization name listed above carries built-in clues that describe the respective configuration. Merely from a hybridization name you can determine: the atomic orbitals (of the central atom) that are most affected by that hybridization the spatial dimensionality the resulting arrangement will have (is it one-, or two-, or three- dimensional?) the name given to each of the hybrid orbitals in the final arrangement in how many directions (orientations out from the nucleus) the hybrid orbitals are arranged EXAMPLES: 3) NO2nitrite ion Ligand atoms? 2O Charge? -1 (one electron extra) 1xN = 1 x 5e = 5e 2xO = 2 x 6e = 12e Ion charge (one extra e) = + 1e Total pool = 18e To octet ligands? Electrons on central atom? Electron dot diagram? 2 x (O) = 2 x 8e = 16e (Of the total pool of 18e, 16e are used to octet ligands) N = 18e - 16e = 2e, or 1 lone pair (N, with its lone pair, and 2 octeted oxo-ligands)

Center atom? N Total electrons?

Electron pair shape and hybridization? trigonal coplanar sp2

Molecular shape? angular

Note: The trigonal-planar electron pair shape indicates that nitrogens atomic orbitals must account for three bonds in two dimensions. This requires three N AOs (2s, 2p, 2p) to combine and rearrange to form three new sp2 hybrid atomic orbitals. Thus the hybridization is sp2 and one -bond is expected though it is not explicitly shown in the diagram. (Review the resonance treatment of nitrite in Assignment 10 if necessary.)
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4)

SnBr2 Center atom? Sn Total electrons?

Tin(II) bromide (stannous bromide) Ligand atoms? 2 Br 1xSn = 1 x 4e = 4e 2xBr = 2 x 7e Ion charge Total pool = 14e = no e = 18e Charge? zero

To octet? Electrons on central atom? Electron dot diagram?

2x(Br) = 2 x 8e = 16e Sn = 18e - 16e = 2e, or one lone pair

Electron pair shape and hybridization? trigonal coplanar sp2

Molecular shape? angular

5)

SnCl62Total electrons? To octet?

hexachlorostannate(IV) ion Ligand atoms? 6 Cl 4e + 6 x 7e + 2e = 48e 6x(Cl) = 6 x 8e = 48e Sn = 48e - 48e = no e (no lone pairs) Charge? -2 (two electrons extra)

Center atom? Sn

Central electrons? Electron dot diagram?

Electron pair shape and hybridization? octahedral sp d

3 2

Molecular shape? octahedral

Note: No -bonds expected because no available empty p atomic orbitals on the central atom. All of Sns valence p AOs, as well as its valence s AO and two of its n-1 d AOs, are involved in a rearrangement to produce six hybrid sp3d2 hybrid orbitals.
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6)

I3-

Triiodide ion Ligand atoms? 2 I 3x7e + 1e = 22e 2x(I) = 2 x 8e = 16e I = 22e - 16e = 6e (three lone pairs) Charge? -1 (one electron extra)

Center atom? I Total electrons? To octet ligands? Electrons on central atom? Electron dot diagram?

Electron pair shape and hybridization? trigonal bipyramidal sp3d

Molecular shape? linear

(lone pairs MUST be placed equatorially in order to obtain correct shape)

7)

UO2+2 Center atom? U Total electrons?

uranyl(VI) ion

(dioxouranium(VI) ion) Ligand atoms? 2 O 2e + 2 x 6e - 2e = 12e 2x(O) = 2 x 8e = 16e U = 12e - 16e = -4e (NO lone pairs) Charge? +2 (two electrons gone)

To octet ligands? Electrons on central atom?

4 electrons MUST come from n-1 d-sub-shells of the uranium atom Electron dot diagram?

Electron pair shape and hybridization? linear sp

Molecular shape? linear

Note: two -bonds predicted (but their effectiveness is limited by the large size of uranium).

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8)

SbCl4Total electrons?

tetrachloroantimonate(III) ion Ligand atoms? 4 Cl 5e + 4x7e + 1e = 34e 4x(Cl) = 4 x 8e = 32e Sb = 34e - 32e = 2e (one lone pair) Charge? -1

Center atom? Sb To octet ligands? Electrons on central atom? Electron dot diagram?

Electron pair shape and hybridization? trigonal bipyramidal sp3d

Molecular shape? teeter

The lone pair on Sb is equatorial, NOT at a axial (up or down) position.

9)

SO3

sulfur trioxide Ligand atoms? 3 O 6e + 3 x 6e = 24e 3x(O) = 3 x 8e = 24e S = 24e - 24e = no e (no lone pairs) Charge? zero

Center atom? S Total electrons? To octet ligands? Electrons on central atom? Electron dot diagram?

Electron pair shape and hybridization? trigonal coplanar sp

2

Molecular shape? trigonal coplanar

Note: One -bond is likely. Each O ligand will share more of its electron octet with the S to provide the central atom with an octet without alteration of the shape. The -bond is delocalized over all four atoms; one-third of the -bond comes from each oxygen ligand.

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Problem Set 30 Be able to define the following terms: hybrid atomic orbital orbital conservation hybridization name

For each of the following formulas: a) construct the electron dot diagram; b) tell what hybridization applies to central atom; c) give diagram and name of both the electron pair shape and the molecular shape; d) tell how many -bonds, if any, the actual molecule should contain. (Follow the procedures outlined in the examples. Mark electron dots clearly.) 1) 2) 3) 4) 5) 6) 7) 8) 9) NF3 , nitrogen trifluoride VO2+ , vanadyl(V) ion IF4 , tetrafluoroiodate(III) ion SnCl62 , hexachlorostannate(IV) ion HgCl3 , trichloromercurate(II) ion TeCl4 , tellurium tetrachloride HOCl (O is central) , hypochlorous acid ClNO (N is central) , nitrosyl chloride H2CO (C is central) , formaldehyde

Do the same for these multi-centered species: 10) CH3CH2OH (bonding sequence is H3C

H C H OH ) , ethanol.

Determine the number of electrons in the electron pool of these molecules & complex ions: CO2 NH4+ HCN (C is central) PO43 SO32 XeF6 PCl4+ NO2 NO3 VOCl3 (V is central) BH4 N3

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Partial answers to P.S. 30: Check your accuracy against the following conclusions. Note: These are not complete answers; yours should also show your reasoning process e.g., the calculation of the electron pool, and accurate depictions of the dot-picture and the electron-pair arrangement (in appropriate geometric style) and the geometric rendition of the entire molecule's shape. The diagrams then serve as basis for deriving the conclusions below. Complete answers may be viewed on the posted answer key on the Chemistry 111 web page. 1) NF3 has total of 26 electrons in the valence pool, resulting in 1 lone pair on the N; electron-pair shape is tetrahedral (corresponding to sp3 hybridization); molecular shape is pyramidal; no -bonding in the final molecule (for the central N already has an octet). 2) VO2+ has a total of only 13 electrons in the valence pool, so no lone pairs can exist on the V; indeed, just to satisfy ligand octets, V must contribute three d electrons (from its inner shell) to the bonding pool; resulting electron-pair shape is linear (sp hybridization); molecular shape is linear; 2 -bonds are plausible (but of limited effectiveness, since vanadium isn't a "second row" element). 3) IF4 has a total of 36 electrons in the valence pool, thus 2 lone pairs remain on the I; electron-pair shape is octahedral (sp3d2 hybridization); molecular shape is square co-planar, with the lone pairs of iodine located opposite from each other; no -bonding in the final molecule (the central I already has more than an octet). 4) SnCl62 has 48 e; no lone pr on Sn; octahedral e-prs (sp3d2 hybridization); octahedral mol.shape; no -bonding. 5) HgCl3 has 24 e; no lone pr on Hg; trigonal co-planar e-prs (sp2); trigonal co-planar mol.shape; 1 -bond is plausible (but of limited effect, since neither element is on"second-row" of P.Table). 6) TeCl4 has 34 e; 1 lone pr on Te; trigonal bipyramidal e-prs (sp3d); teeter mol.shape; no -bonding; the lone pair on Te must be placed equatorially, not at a polar position. 7) HOCl has 14 e; 2 lone prs on O; tetrahedral e-prs (sp3); angular mol.shape; no -bonding. 8) ClNO has 18 e; 1 lone pr on N; trigonal co-planar e-prs (sp2); angular mol.shape; 1 -bond is necessary. 9) H2CO has 12 e; no lone pr on C; trigonal co-planar e-prs (sp2); trigonal co-planar mol.shape; no -bonding. 10) CH3CH2OH has three central atoms: C1(at left), C2(at center), O(at right). Around C1 , no lone pr on C1 ; tetrahedral e-prs (sp3); tetrahedral mol.shape; no -bonding. Around C2 , no lone pr on C2 ; tetrahedral e-prs (sp3); tetrahedral mol.shape; no -bonding. Around O , 2 lone prs on O; tetrahedral e-prs (sp3); angular mol.shape; no -bonding. (To design an overall molecular diagram, tilt the tetrahedral shapes so that C-C-O "backbone" lies flat.)

Electron pools of the molecules: Electron pools of complex ions:

16e; 10e; 50e; 17e(there is an unpaired e on N here); 32e. 8e; 32e; 26e; 32e; 24e; 16e; 8e.

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