tro3 lecture 24
TRANSCRIPT
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Chapter 24Transition
Metals andCoordinationCompounds
2007, Prentice Hall
Chemistry: A Molecular Approach , 1 st Ed. Nivaldo Tro
Roy KennedyMassachusetts Bay o!!unity olle"e
#ellesley Hills, M$
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%e!stones
&the colors o' ru(ies and e!eralds are (oth dueto the )resence o' r *+ ions the di''erence liesin the crystal hostin" the ion
-o!e $l *+ ions
in $l 2 * arere)laced (y
r *+
-o!e $l *+ ionsin
Be *$l 2/-i * are re)laced (y
r *+
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Pro)erties and Electron on'i"urationo' Transition Metals
& the )ro)erties o' the transition !etals are si!ilar toeach other
and very di''erent tot he )ro)erties o' the !ain "rou) !etals
hi"h !eltin" )oints, hi"h densities, !oderate to very hard,and very "ood electrical conductors& in "eneral, the transition !etals have t o valence
electrons e are 'illin" the d or(itals in the shell (elo the valence
%rou) 1B and so!e others have 1 valence electron due to3)ro!otion4 o' an electron into the d su(level to 'ill it'or! ions (y losin" the ns electrons 'irst, then the / n 1 d
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$to!ic -i5e
&the ato!ic radii o' allthe transition !etalsare very si!ilar
s!all increase in si5edo n a colu!n
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6oni5ation Ener"y
&the 'irst ioni5ationener"y o' the
transition !etalsslo ly increasesacross a series
&third transition seriessli"htly hi"her 1 st 6E
trend o))osite to!ain "rou) ele!ents
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Electrone"ativity
& the electrone"ativity o'the transition !etalsslo ly increases acrossa series
e ce)t 'or last ele!ent inthe series
&electrone"ativitysli"htly increases do nthe colu!n
trend o))osite to !ain"rou) ele!ents
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idation -tates
&o'ten e hi(it !ulti)le o idation states&vary (y 1&hi"hest o idation state is "rou) nu!(er 'or *B to 7B
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oordination o!)ounds& hen a co!)le ion co!(ines ith counterions to
!a8e a neutral co!)ound it is called a coordinationcompound
& the primary valence is the o idation nu!(er o' the!etal
& the secondary valence is the nu!(er o' li"ands (ondedto the !etal
coordination number
&coordination nu!(er ran"e 'ro! 2 to 12, ith the !ostco!!on (ein" and 9
o l * H2 : ; o/H 2 < l*
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o!)le 6on =or!ation&co!)le ion 'or!ation is a ty)e o' >e is acid?
(ase reaction
&a (ond that 'or!s hen the )air o' electrons isdonated (y one ato! is called a coordinatecovalent bond
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>i"ands ith E tra Teeth
&so!e li"ands can 'or! !ore than one coordinatecovalent (ond ith the !etal ato!lone )airs on di''erent ato!s that are se)arate enou"hso that (oth can reach the !etal
&chelate is a co!)le ion containin" a!ultidentate li"and
li"and is called the chelating agent
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E@T$a Polydentate >i"and
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o!)le 6ons ith Polydentate >i"ands
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%eo!etries in o!)le 6ons
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Na!in" oordination o!)ounds1 deter!ine the na!e o' the nonco!)le ion2 deter!ine the li"and na!es and list the! in
al)ha(etical order
* deter!ine the na!e o' the !etal cation9 na!e the co!)le ion (yA
1 na!e each li"and al)ha(etically, addin" a )re'i in 'ront o'each li"and to indicate the nu!(er 'ound in the co!)le ion
2 'ollo ith the na!e o' the !etal cation
rite the na!e o' the cation 'ollo ed (y the na!e o'the anion
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o!!on >i"ands
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o!!on Metals 'ound in$nionic o!)le 6ons
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6so!ers
&Structural isomers are !olecules that have thesa!e nu!(er and ty)e o' ato!s, (ut they are
attached in a di''erent order &Stereoisomers are !olecules that have the sa!e
nu!(er and ty)e o' ato!s, and that are attached
in the sa!e order, (ut the ato!s or "rou)s o'ato!s )oint in a di''erent s)atial direction
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>in8a"e 6so!ers
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E . 29. @ra the structures and la(el the ty)e'or all iso!ers o' ; o/en
2l
2
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)tical 6so!ers
&optical isomers arestereoiso!ers that are
nonsu)eri!)osa(le !irrori!a"es o' each other
; o/en *
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E 29.7 @eter!ine i' the cis?trans iso!ers o'; o/en
2l
2
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Bondin" in oordination o!)ounds
Dalence Bond Theory
& (ondin" ta8e )lace hen the 'illed ato!ic
or(ital on the li"and overla)s an e!)ty ato!icor(ital on the !etal ion
&e )lain "eo!etries ell, (ut doesn t e )lain
color or !a"netic )ro)erties
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Bondin" in oordination o!)ounds
rystal =ield Theory& (onds 'or! due to the attraction o' the electrons on the
li"and 'or the char"e on the !etal cation&electrons on the li"ands repel electrons in the
unhy(ridi5ed d or(itals o' the !etal ion& the result is the ener"ies o' or(itals the d su(level are
s)lit& the di''erence in ener"y de)ends the co!)le and 8inds
o' li"andscrystal 'ield s)littin" ener"ystron" 'ield s)littin" and ea8 'ield s)littin"
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-)littin" o' d r(ital Ener"ies due to
>i"ands in a ctahedral o!)le
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-tron" and #ea8 =ield -)littin"
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o!)le 6on olor
&the o(served color is the co!)li!entary color o'the one that is a(sor(ed
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o!)le 6on olor and
rystal =ield -tren"th&the colors o' co!)le ions are due to electronic
transitions (et een the s)lit d su(level or(itals
&the avelen"th o' !a i!u! a(sor(ance can (eused to deter!ine the si5e o' the ener"y "a)
(et een the s)lit d su(level or(itals
E )hoton : h : hcF :
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>i"and and
rystal =ield -tren"th&the stren"th o' the crystal 'ield de)ends in lar"e
)art on the li"andsstron" 'ield li"ands includeA N G N 2 G en NH *
ea8 'ield li"ands include H 2 H G = G l G Br G 6 G
&crystal 'ield stren"th increases as the char"e onthe !etal cation increases
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Ma"netic Pro)erties and
rystal =ield -tren"th& the electron con'i"uration o' the !etal ion ith s)lit d
or(itals de)ends on the stren"th o' the crystal 'ield
& the 9th
and th
electrons ill "o into the hi"her ener"y d x2- y2 and d z2 i' the 'ield is ea8 and the ener"y "a) is s!all leadin" to un)aired electrons and a )ara!a"neticco!)le
& the 9th
thru th
electrons ill )air the electrons in the d xy ,d yz and d xz i' the 'ield is stron" and the ener"y "a) is lar"e leadin" to )aired electrons and a dia!a"netic co!)le
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>o -)in I Hi"h -)in o!)le es
)ara!a"netic
hi"h?s)in co!)le
dia!a"neticlo ?s)in co!)le
only electron con'i"urations d 9, d , d , or d 7 can have lo or hi"h s)in
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Tetrahedral %eo!etry andrystal =ield -)littin"
& (ecause the li"and a))roach interacts !orestron"ly ith the )lanar or(itals in thetetrahedral "eo!etry, their ener"ies are raised
&!ost hi"h?s)in co!)le es
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-Cuare Planar %eo!etry andrystal =ield -)littin"
&d J !etals&the !ost co!)le s)littin" )attern&!ost are lo ?s)in co!)le es
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$))lications o'
oordination o!)ounds&co!!ercial colorin" a"ents
)russian (lue : !i ture o' he acyano=e/66 and =e/666
in8s, (lue)rintin", cos!etics, )aints& (io!olecules
)or)hyrin rin"cytochro!e he!o"lo(inchlor)hyll
chloro)hyll
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$))lications o'
oordination o!)ounds&car(onic anhydrase
cataly5es the reaction (et een ater and 2
contains tetrahedrally co!)le ed n 2+
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$))lications o'
oordination o!)ounds&@ru"s and Thera)eutic $"ents
cis)latin
anticancer dru"