Molecular Structure Brady & Senese, 5th Ed Personal Use Only Index 9.1. Molecules are three-dimensional with shapes that are bui lt from five basic arrangements 9.2. Molecular shapes are predicted using the VS!" model 9.#. Molecular s$mmetr$ affects the polarit$ of molecules 9.%. Valence bond theor$ explains bondi ng as an overlap of orbitals 9.&. '$brid orbitals are used to explain experimental molecul ar geometries 9.(. '$brid orbitals can be used to explain multiple bonds 9.). Molecular orbital theor$ explains bon ding as constructive interference of atomic orbitals 9.*. Molecular orbital theor$ uses delocali+ed orbitals to des cribe molecules with resonance structure Personal Use Only 9.1 Molecules are three-dimensional with shapes that are built from five basic arrangements # ,he -ive .asic lectron /rrangements lectron 0omains Shape lectron !air 1eometr$ 2 linear # trigonal planar % tetrahedral Personal Use Only 9.1 Molecules are three-dimensional with shapes that are built from five basic arrangements % ,he -ive .asic lectron /rrangements 23ont.4 lectron 0omains Shape lectron !air 1eometr$ & trigonal bip$ramidal has e5uatorial and axial positions. ( octahedral has e5uatorial and axial positions Personal Use Only 9.1 Molecules are three-dimensional with shapes that are built from five basic arrangements & 6earning 3hec78 Identif$ ,he lectron !air 1eometr$ -or ach 3enter tetrahedral tetrahedral ,rigonal bip$ramidal Personal Use Only 9.1 Molecules are three-dimensional with shapes that are built from five basic arrangements ( 9our ,urn: ;hat is the electron pair geometr$ for 3 in 3< 2 = /. linear .. planar triangular 3. tetrahedral 0. trigonal bip$ramidal . octahedral Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model ) .onding 0omains /nd >on-bonding 0omains ? Bonding domains are shared between nuclei ? Non-bonding domains are not shared between nuclei-the$ exert a greater electrical field ? "epulsion leads non-bonding domains to occup$ larger space ? ,he basic shapes are distorted b$ non-bonding domains to create the molecular geometry Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model * ,rigonal !lanar Molecular 1eometries .onding 0omains >on-bonding 0omains Molecular 1eometr$ # @ trigonal planar 2 1 bent Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 9 ,etrahedral Molecular geometries Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 1@ ,rigonal .ip$ramidal ? Equatorial 2e4 positions are substituted first ? ,his is because the eAe bond angles are 12@BA while aAe bond angles are onl$ 9@B Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 11 <ctahedral 1eometries ? /ll bond angles are 9@B ? Axial positions are substituted first Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 12 6earning 3hec78 Identif$ the molecular geometr$ for each center ,rigonal p$ramidal >on-linearA bent 6inear Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 1# 9our ,urn: ;hich re5uire more space= /. bond pairs .. lone pairs 3. both are the same Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 1% 9our ,urn: ;hich bond angles are closer in a trigonal bip$ramidal structure 2aC axialD eCe5uatorial4= /. a-a .. a-e 3. e-e 0. the$ are all the same Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 1& 9our ,urn: ;hich bond angles are closer in a trigonal bip$ramidal structure 2aC axialD eCe5uatorial4= /. a-a .. a-e 3. e-e 0. the$ are all the same Personal Use Only 9.2 Molecular shapes are predicted using the VS!" model 1( 9our ,urn: ;hat is the molecular geometr$ of 3 in 3' % = /. 6inear .. S5uare planar 3. S5uare p$ramidal 0. ,etrahedral . >one of these Personal Use Only 9.# Molecular s$mmetr$ affects the polarit$ of molecules 1) !olar Molecules /re /s$mmetric ? ,o determine the polarit$A draw the structure using the proper molecular geometr$ ? 0raw the bond dipoles ? If the$ cancelA the molecule is non-polar ? If the molecule has uneven dipole distributionA it is polar Personal Use Only 9.# Molecular s$mmetr$ affects the polarit$ of molecules 1* 6earning 3hec78 !olar or non-polar= polar >on-polar polar Personal Use Only 9.# Molecular s$mmetr$ affects the polarit$ of molecules 19 9our ,urn: 3' 2 3l3' 2 3l 2freon-1&@4 is li7el$ to be8 /. !olar .. non-polar 3. cannot tell Personal Use Only 9.# Molecular s$mmetr$ affects the polarit$ of molecules 2@ 9our ,urn: .en+o$l peroxide 2used in common acne medications4 is li7el$ to be8 /. polar .. non-polar 3. cannot tell Personal Use Only 9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 21 Valence .ond ,heor$ ? ' 2 bonds form because atomic valence orbitals overlap ? '- involves overlaps between the s orbital on ' and the 2p orbital of - 1s 1s 1s 2s 2p Personal Use Only 9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 22 V. ,heor$ /nd ' 2 S ? /ssume that the unpaired e - in S and ' are free to form a paired bond ? ;e ma$ assume that the '-S bond forms between an s and a p orbital Personal Use Only 9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 2# 9our turn: /ccording to V. ,heor$8 ;hich t$pe of overlap does not occur in .' # = /. s-s .. s-p 3. p-p 0. none of these Personal Use Only 9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 2% 9our turn: /ccording to V. ,heor$8 ;hich orbitals overlap in the formation of >' # = /. s-s .. s-p 3. p-p 0. none of these Personal Use Only 9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 2& 0ifficulties ;ith V. ,heor$ So -ar8 ? Most experimental bond angles do not support those predicted b$ mere atomic orbital overlap ? -or example8 3 1s 2 2s 2 2p 2 and ' 1s 1 ? xperimental bond angles in methane are 1@9.&B and all are the same ? p orbitals are 9@B apartA and not all valence e - in 3 are in the p orbitals ? 'ow can multiple bonds form= Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries 2( '$bridi+ation ? ,he mixing of atomic orbitals to allow formation of bonds that have realistic bond angles ? ,he new shapes that result are called Eh$brid orbitalsF ? ,he number of h$brid orbitals re5uired C the number of bonding domains G the number of non-bonding domains on the atom Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries 2) ;hat Shall ;e 3all ,hese >ew <rbitals= ? Since we have annexed the spaces previousl$ defined b$ atomic orbitalsA we name the h$brid as a combination of the orbitals used to form the new h$brid ? <ne atomic orbital is used for ever$ h$brid formed 2orbitals are conserved4 Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries 2* '$brids -rom s H p /tomic <rbitals ta7e VS!" 1eometr$ '$brid /tomic <rbitals Ised lectron 1eometr$ sp # s G p x G p $
G p + ,etrahedralA bond angles 1@9.&J sp 2 s G p x G p $ ,rigonal planarA bond angles 12@ J sp s G p x 6inearA bond angles 1*@ J Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries 29 6earning 3hec78 Identif$ ,he '$brid <rbitals In ,he -ollowingA .ased <n ,heir VS!" 1eometr$ Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries #@ 0etermining h$bridi+ation8 1. expand all valence electrons within the valence energ$ level. -or 3A for example this means8 ? 2sKL 2p K M K MMM N'eO2s 2 2p 1
? .ecomes8 ? 2sK 2p K M K M K MM Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries #1 '$bridi+ation ? 2. >ow anal$+e the bonding and lone pair needs. 9ou will need to use one h$brid orbital for ever$ bonding domain and one for ever$ non-bonding domain. ? -or 3 in 3' % we see that there are % attached atoms and no lone pairs on 3. ,hus we will need % h$brid orbitals. H H H H C Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries #2 '$bridi+ation 2sp # 4 ? #. >ow anal$+e the atomic orbital needs. 9ou will need to use one atomic orbital for ever$ h$brid orbital . ? -or 3 in 3' % we will need % h$brid orbitals. ? 2sK 2p K M K KM ? ,husA we will need to use all valence level atomic orbitals available to us. ? 22sK 2p K M K M K4 ? S G p G p G p P % new e5uivalent Esp # F orbitals. H H H H C Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries ## .onding in 3' %
? ,he % h$brid orbitals are evenl$ distributed around the 3 ? ,he ' s-orbitals overlap the sp # h$brid orbitals to form the bonds. H H H H Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries #% s H p h$brid shapes Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries #& 9our ,urn: In the compound 3' # <'A what is the expected h$bridi+ation on <= /. sp .. sp 2 3. sp # 0. < does not h$bridi+e Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries #( xpanded <ctet '$bridi+ation ? 3an be predicted from the geometr$ as well ? In these situationsA d orbitals are be needed to provide room for the extra electrons ? <ne d orbital is added for each pair of electrons in excess of the standard octet Personal Use Only 9.& '$brid orbitals are used to explain experimental molecular geometries #) xpanded <ctet h$bridi+ation Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds #* .onding ,$pes ? ,wo t$pes of bonds result from orbital overlap8 ? sigma bonds
from head-on overlap
lie along the bond axis
account for the first bond
? pi bonds
from lateral overlap b$ adQacent p or
d orbitals
pi bonds are perpendicular to bond
axis
account for the second and third
bonds in a multiple bond Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds #9 '$bridi+ation of 3 in 3' 2 < < ' ' 3 1. xpand all valence electrons within the same energ$ level. -or 3A for example this means8 ? 2sKL 2p K M K MMM N'eO2s 2 2p 1
? .ecomes8 ? 2sK 2p K M K M K MM Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds %@ '$bridi+ation of 3 in 3' 2 < < ' ' 3 ? 2. >ow anal$+e the bonding and lone pair needs. 9ou will need to use one h$brid orbital for ever$ attached atom and one for ever$ lone pair. -or 3 in 3' 2 < we see that there are # attached atoms and no lone pairs on 3. ,hus we will need # h$brid orbitals. Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds %1 sp 2 '$bridi+ation ? #. >ow anal$+e the atomic orbital needs. 9ou will need to use one atomic orbital for ever$ h$brid orbital. -or 3 in 3' 2 < we will need # h$brid orbitals.
2sK 2p K M K KM
,husA we will need to use # valence level atomic
orbitals available to usA and one of the p orbitals will remain.
22sK 2p K M K 4 M K
s G p G p P # new Esp 2 F orbitals.
;e are left with one unh$bridi+ed orbital.
Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds %2 >ow anal$+e the <8 ? N'eO 2s 2 2p 2 22sKL 2p K LM K 4 M K ? ,he < is has one bonding domain and 2 non- bonding domainsA hence it will re5uire three h$brid orbitals. ? >o expansion neededA as one unpaired e - is available to bond. Ise # atomic orbitals to ma7e the new h$bridsA sp 2 . 22sKL 2p K LM K 4 M K ? /gain we are left with one unh$bridi+ed p orbital < ' ' 3 Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds %# !i .onding Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds %% 'R3S3 R' ? ach 3 has a triple bond and a single bond ? "e5uires 2 h$brid orbitalsA sp ? unh$bridi+ed p orbitals used to form the pi bond Personal Use Only 9.( '$brid orbitals can be used to describe multiple bonds %& 9our ,urn: 3onsider a molecule of 3' # 3< 2 '8 'ow man$ pi bonds are there in the molecule= /. 1 .. 2 3. # 0. % . ,here are none Personal Use Only 9.) Molecular orbital theor$ explains bonding as constructive interference of atomic orbitals %( Molecular <rbital ,heor$ ? Modification of V. theor$ that considers that the orbitals ma$ exhibit interference. ? ;aves ma$ interfere constructivel$ or destructivel$ ? .onding orbitals stabili+eA antibonding destabili+e. Personal Use Only 9.) Molecular orbital theor$ explains bonding as constructive interference of atomic orbitals %) M< diagrams ? Show atomic energ$ level diagram for each atom ? Show molecular orbitals 2bonding and antibondingT4 ? 1 M< for each /tomic orbital. ? Show electron occupanc$ of the orbitals. Personal Use Only 9.) Molecular orbital theor$ explains bonding as constructive interference of atomic orbitals %* -illing M< diagrams 1. lectrons fill the lowest-energ$ orbitals that are available. 2. >o more than two electronsA with spins pairedA can occup$ an$ orbital. #. lectrons spread out as much as possibleA with spins unpairedA over orbitals that have the same energ$. %. .ond order C e - in bonding orbital-e - in nonbonding orbitals. Personal Use Only 9.) Molecular orbital theor$ explains bonding as constructive interference of atomic orbitals %9 0iatomic M< diagrams differ b$ group ? /4 I - V .4 VI-VIII/ Personal Use Only 9.) Molecular orbital theor$ explains bonding as constructive interference of atomic orbitals &@ M< diagrams 0raw the expected M< diagram for8 ? < 2 ? .' ? 'e 2 ;hich are not li7el$ to existA and wh$= Personal Use Only 9.* Molecular orbital theor$ uses delocali+ed orbitals to describe molecules with resonance structures &1 0elocali+ed lectrons ? 6ewis structures use resonance to explain that the actual molecule appears to have several e5uivalent bondsA rather than different possible structures ? M< theor$ shows the electrons being delocalized in the structure Personal Use Only 9.* Molecular orbital theor$ uses delocali+ed orbitals to describe molecules with resonance structures &2 3< # 2- '$bridi+ation ? 3arbonate has three e5uivalent resonance structures. ;hat are the$A and which electrons are delocali+ed= ? 0raw the h$brid molecule to indicate the delocali+ation of these electrons. Personal Use Only