Russian No..!, 1994.,-pn. Journalof Inorganic.Chemistry.U.oL-J9, I'142--.1448. Tmnslatedfrom Zumal Neorganicheskoi Khimii,Vol. 39, No.9, 1994, pp.

I5I0 - 1516. Original RussianTexCopyright @1994 by Naanutdinova,Shtyrli4 Kukushkina, Zakharov. Englishftanslation Copyight @194 by MAIIK Hayca/Inerpeiodica Publishing(Russia).

COORDINATION COMPOUNDS

ComplexFormation and Ligand Exchange in AqueousSolutions of Oxovanadium(ry) with Amino Acids

G. A. Nazmutdinova,V. G. Shfyrlin, O. V. Kukushkina, and A. V. Zakharov
KazanStateUniversity,ul. Lenina 18,Kazan,420008Tatarstan,Russia Received Januarv 12.1994 Abstract - Complex formation of oxovanadium(IV)with optically activeand racemicforrrs of amino acids (Lt! = glycine,D, L-c-alanine,D-, Dl-valine, L-, Dl-proline; LH2 = D-, Dl-aspartic acid,L-, Dl-glutamic acid) was${:a by spin-latticenugl-ear mag-netic relaxationand spectrophotometric methodsin the pH range from 1 to 1j).The-c_o_mpositions and the stability constants of the complexes VOLH, VO(LH)2, VOL, VObfI, forall ligandsL, and of VOLH2,-for asparticd YOle,.09)ZI4!O4)?!ana.-Vpl2(OU) were detennined glutamic-acids. TheLH2 andLH forms arenot only coordinated to thecarboxygroups, but alsolinkeAiy hydro-yl oxygenatomthrough ammoniumq9up. Two OH- groupsin the (VO)fu(OH)z tomgenbondswith-the-an plex perf-orrra bridging function, thusprgviding efficientgtilgnoryrlgnetic spinexchange. The hy-droxy-group in VOIa@II) occupiesan equatorialposition, andoneof the ligandsL is axially-equatorially cooiainatO] Stereoselectivitywas only observedfor the formation of a VOIaH complexwith a tidentate ligand (asparate). H9re,the optically ctivefonn yields a more stablecomplexthandoesracemate. This is a reslt of the proton migration betweenthe coordinatedligands,with alternatingrealizationof their maximumpolydentant6character.The kinetics of ligand exchange in sslltio!! olvof2 and VOIa(OH) complexes wasinvestigatedby m_etho{ of spin-spin nuclealmagnetic relaxation. TheL-exchange procee reactions by an associativJmechinism similar to that known in.copper@)co.mpounds. However,the fast migrationof the carboxygroup of the coordinated ligandsbetween the axial andthe equatorial positionsproduces distinctionsof the excliangmechanismof the oxovanadium(IV)complexes frorn-thatof the copper@)complexes.

Comparison of the structure, stability,and lability of complexes of copper(If)andoxovanadium(IV) is of considerableinterest for coordinationchemistry,as they bearthe samechargeand haveremoteaxial positions, while oxovanadium(IV) contains a multiply bonded oxygenatom. Of all the amino acid complexes of the transition 3d-metals,the stability and lability of copper(If compounds were most comprehensively investigated[1, 2]. T}ae coordinationcompounds of oxovanadium(IV) were studiedin much 1"rs dsteil. Thus, the compositionsand the stability constantsof the complexesformedover a wide pH mngewere only investigatedfor the systems of oxovanadium(IV) with glycine 41, L-a-alanine L-serine L-threonine 13, [5], [6], [6], L-cysteine [7], L-aspartic acid [8], and L-glutamic acid [9]. The ligand exchangereactionswere studied only in glycinatesolutionsof oxovanadium(tV) [4, 10]. In this work, we usedthe methodof nuclearmagnetic relaxationof water protons [11] to investigate complex formation and ligand exchangein oxovanadium(IV) solutions(pH 1 - 10) containingoptically activeandracemicforms of aminoacids(LH = glycine (GlyH), Dl-s-alanine (AlaH), D-, Dl-valine (ValH), L-, Dl-proline (ProH); LHz = D-, Dl-aspartic acid (AspH), L-, Dl-glutamic acid (GluHt). Spectrophotometry wasusedasa supplementary method. The aim . of the investigationwas to determinethe factors that governthe stability and lability of the amino acid com-

plexesof oxovanadiumfiV)depending on the natureof the ligandsandthe centralion. EXPERIMENf,AL We usedoxovanadium(IV)sulfate and chloride of analyticalgrade.The concentration of the metal in the solution was determinedpermanganometrically. The amino acids were suppliedby Reanal,except for the analyticalgradeglycineandDl-valine. The aminoacid concentration was established by means of precise welghling. The mediumacidity was adjustedby using analyticalgrade HCl andKOH solutions.The saltbackgroundwaskeptconstant at 1 moL/lusing reagent grade potassium chloride. The solutions werethermostated, at298 + I K. The pH wasmeasured with a pH 673M meterwith an error g + 0.42logarithmic not exceedin units.The spin-lattice (fJ and spin-spin(?) relaxationtimes of the water protons were measuredon a coherent pulsed NMR (operated spectrometer at a frequencyof 15MHz) with an accuracy of +2 and13Vo,respectively. The paramagnetic contribution (il to the relaxation rate (I I T\2) wasdetermined by subtracting the LI Tr,, valuesmeasured in thepresence andin the absence of the paramagnet. The optical densities of the solutionswere measured on an SF-46spectrophotometer.

t442

COMPLH( FORMATION AND LIGAND EXCHANGE x 104, V(mols) was (rlcwTzp) Theoxidationof vanadium(V) t9 ynadium($ The t or""",J"6qt*s ;qo1 ttiroug!-t!^solutions' during ielaxationtimes ot tniilutions wremeasured 30 using pt"p-ation uri"i -specially ffi-;'";t-11 of value 2.0 8.01 riJ .rot9a.u-g"les' The constant ^ with solutions the of stability for o l cntenon a as served E I to oxidation. . respect associated qd +" In orderto mrmmizehydrolysis andto fix theprotonated f ' l o*iir*ou*uaiom(rD O I ti"titv produts at low ; ;i";;J-rwiricri i +.0{1.0 lieandcontentconcentrations),-waused.hiehamino of rot obseivation (0.f:i;r'ni' aidconcentrations 3 l 10 coidex formation' ^we varied the ;;;iffJear The from 0'005t9 0'07 moVl' metalion .on""nt utrl'justified electrolyte.was uu"tgtound v l Ki ;ltt" ;f

1443

I I

s l
I

complexes ti,"; i dt-ci- is form very weak equilibthe significantlv iii ;;-fij, oot ihining acids' amino tne ivitrr ?ormation ;d;di ^*;;;ositions stabiland.their of thecomplexes podmathematically by wereoetermined itv constants
of

ll CMTV Q)' U CvT2o(2)' ande (3) verFig. 1. Parameten Cvq = 2'0 x system; suipH in ttreoxouanaOiumfiVFgtycine -relaxation ;'itiPEsse-piolru*p?'k"s"[1-1]]lledenendence = 550nm' coefficient = l' 10-2moVl,Cq, = 1.0moill, C6q 1'0 moUl' the molar sprn-lattice

of the.concentrations iil ciri,,i " itt" *i* ptt qg as of the-dependence theg;d wett il;dfud pH ttre on. Qgt;'1 G "itin"rioi co"m"i"nt9 into,account the
; t;;i ;;"iffi;;-

T=298K. (LlCyTz) x 10-3,V(mols)

wecalcutneeiamnlg isee ii""i-ri,s -r1 Tg' i-)' ligand the for th" rut" "onstall-s
latedby leastsquarei or almost in the-rygi919f-"s19w r"u.trooJ substitution

Taking iilustrations)' of the u" tn a"#ee of aclmulation

;;ilJ;;;'s.;'

relaxation or trt" ffi'* ipin-i^pin ";;;;t concentrapH ot11'" medium the on ;i{;;aIinrr,) ion- = acidic anions acid ffi;irh"fio Qg'+l'The calcufor required acis' .i' tli *ino ji .i"tt-t*f of LH prameters ffih;;avnamic a kineticresPeg- x il'tri;;;i-u6tto*ea from[14] and[1]'an Eleko

Se tlli (PII6.- 10)rrom coeffi-

8.0
-'-

.!a fr ll

were carriedoutusing ;" Ti;" calculations -28 microcomPuter' tronika D3

4.0

> 2.0

werfoundfor "o"i#il' oTugt* constanls set fg.t ;iltfi; uy u t.oiotialsearch thgminimal pS describe to n"tetsary foims 4" oi"tpr"* 9:ry1; ot Theathematical.description ;;;i (ii C*Tr,r).
svstemwas "tifiU.iu it th oilovanadium(Iv)-glycine logarith-

RESUUN AND DISCUSSION The Composition and stabitity of complexes'

uv fi'i"'..-tio *i"ttiin 0'05 ;#;t eorypleTes of tire tt"uititv constants ;;;i6i 9t:Y ande of (|lQu{ro) "?"r,i"'riompn depehdences ( versus r' -) c." the U calcufrom and 1iFlg.b ;A;tie-ttantf, of protonated complexes given in Table yere pry LH2' and LH forms versus '2' the to -i;";;;-a;;iH.ti'^a"F cv and i;r f;ri;-*"ta'uonaitig the of results nnfl r!' pramt'*a' trii stability The H*' nd L ;"Y;y;;;. iooiuiaua of other ;t;" = (V-O)2IaH-2 complexes. calculations*" gtu"n it Table 1' Innodugtion "i"ir-of tft" deprotonated
;;i;;};;t, ;i"; 6"tiLt tttoselisted in Thblef into the of ;.ttt"" - noi i*ptou" the description

(/'-2) andsoin-spin of spin'lattice Fie.2.Molarcoeffrcients (3.4relaxatio"i"th.;;di;;Cv;tl;aspaiti-9a9! acid(2'4) svstems; i;: ji ;d "i;"anadium(IVID-aspartic 0'1moVl (/' 3) and = moVl 0'2 C4sp moVl, t 10-3 '^ = S.O T;298K' l'0 moVl; (2',i),CKa=

,f" ;#;t'fi

estiin thiswork' the other"o-pr"*",1o*-too ima[ for.a reliable constants ".s itb.ol *ui notstudied stabiliry The constants' tJr-iGiulitv
RUSSIAN JOIJRNAL OF INORGANIC CIIEMISTRY VoL 39 No' 9 1994

of accumultion "i"".."1

irurto;d

j;Ly*,fr-''l/I'Yil'k ]: *?'"?3*.u:

reprevol4H-r=vo-lr(o-s)are

1444
CT

NAZVIUTDINOYA Ct AI.

0.5

of the complexforms in Fig. 3. Diagramof the distribution-with, D-aspartic acid oxovanadium(IV) solutions ot 2)' Fig' for as itG"nAtiont arettle same x 104, V(mol s)

(U C{2)

1.8

of the corresponding by deprotonation itancecaused in large ligands of "*i"-n *A arninolroups -present po;s1 tfre limits ally ip princ - rlrttit .io.t-t*" in ifiii* ot ttt. potentiomtricirethod employed are measurements relaxation t+. S. A,91.Ttremagnetic irJ. it".ittese limitions, andthis is the main advanthe tille syslqTs' in investigating i"n"f tt it technique the staqility above, mentioned w?itt"i* iiceitions I have Table in listed forms cmplex the of "ontt-tt for the first time' bnreliably determined The analysisof the stability constantsof the comof"i"t, a"paiog on their compositionand the nature yields information on their figands, i;h;*Jt"n. strudure. ligandsL'VqL' with deprotonated The complexes CuL corresponding the tan ana-VOU u." l"st stable conthe time' same the at [1]; C"L" cmpounds formLH protonated the of aaoitin tJt't"i.pdiii lett"ioe, o-anine, valine, proline) to oxovanail;irD ;; tars; ritanfor additionto copper(Il) t15l' trom that' aside assuming by -the ftrit iu.t.*, bexplained the grouP of carboiv of .^ri"tiJlt"iai"tion complexes'.an oxovanadium(IV)LH in the ;;t;" the aOiooA hydrogen bond is formed between (-vl) bonded multiplv the and ;;i"*ooplrlg ti'tti"tt carries a very large negative ;;;;;-;,"-,chrle(-0.60)t161. Aspartic and glutamicacidscontain-anadditional ."riy ;;up-,-w"tricttmakesthem capableof coordinationiobxovanadium(IV)in the LH2 form in a manabovefor the other LH to that described ;;;;t*td by *ias. The microequilibrium establishedt"LH2 of goups betweencarboxy ;;t-"tdiuting '"ri*r .rorc iasic.;ties rendersthese groupg eqgalv the basicity oJ-tlt-e Because .uoUi" of coordination.

(pKz=3'95tll) of AspH2 "ai,i"J.-u"iv group the

*O Cfoff, (pKz= 4.28 ill) is higherthanthat of

1/ CMT2r.onthe pH of tlte parameter Fig. 4. Dependences Dle-alanine (/)' with in solutions of oxovandium(IV) Dl-proline (4); and (rj, D;"tti"e'(3)' ttil;;;""id moUl;CG1" i."*on; Cvil= 0.50 moVt;C*o 10'50 molll;T=298K' 1'0 Cssl= l'0 moUl;

6i":ls

c61^= 41; *ol,n(/, 3),5'0x roa 12' * ro- =

(Table 1) The values of the stability constnts with the-literaturedata exhibit satisfactoryagreement and ior elvcine [4], L-cl-alanine[5], and L-aspartic were discrepancies Significant L-nrl"rni. alis [9, 9]. conoUi"*"Jonly foi thJ estimatesof the stability and VO(LH)z with compositions ,t, of complexes comthese because Virn-,. This is not surprising capacpf"*-*ltomulate in the rigion of largebuffer

:r" .lirprrs (pKr3 2.s lr,14l), thestabitv of VOAspHf" and VOGluHl. is co:respondingly ol"lipUuf: ggino of complexeq triehttth**t stability (table 1)- upon VotH G-io*p.ition ;r;-;i' additionaltunctionalgrolPl become ;;;d"ti"", ttrestability hence, J"5Ji" i"itaitation, and, 9fcon1 glwamrc of form LH the pGx.scontaining $Partic.ano 1)' to pK2(Table pioportionally increases cids comof the coordination The stabilityconstants arnino Vr- a voq containing ooon-t .4lrhatic in = 9'7- 9:s [ 14])decrease (p|K, "r a"* basicitv Ji-t sequence This vaF' Alr, orga;oiciv-, t;;G; of olttt ionditionsfor solvation ;"il;il;;r" alithe side of size the in "t" in"t an "tnoi"*"t with 'iiiJ lil. f[" nien"t stabilitvof thecorresponding its high basicitv pioTi"" results-from ;;j";;;*ltrt (pKi= 10.s8 t14J). VOL and of the complexes The stabilityconstants The glutamates' for those VOL2for uspai'tateJixceed to voGlu canbe tuiritv of VoAsp compared ttigtt-.it
VoL 39 No' 9 1994

RUSSIAN JOURNAL OF INORGANIC CHEMSTRY

COMPLEX FORMATION AND, LIGAND EXCHANGE

L445

at formed in oxovanadium(rv)-aminoacid (LH, LH) systems of complexes Table 1. compositionsand stability gonstants of 1 mol/l KCI g K *itt, a bckground

logF
Complex VOLH vo(LH)2 VOL vot2H

Glv-

DL-g-Ala-

D-Val

DL-Val-

L-Pro-

DL-Pro 1.05 t 0.03 + 0.03 1.65 + 0.13 7.28 7.99!0.07 + 0.03 13.11 r 0.03 6.30 + 0.05 4.51
DL-

voL
cvo)2l2H-2 vot2H-l
Complex

+ 0.03 1.10 t 0.03 1.15 + 0.05 + 0.03 1.69 1.70 + 0.10 6 . 8 1 1 0 . 0 9 6.64 + 0.03 + 7.48 7.57 0.03 + 0.03 0.03 12.06 t2.23+ + 0.03 + 0.03 5.38 5.71 + 0.08 3.04 0.05 3.44+
L-Glyz-

+ 0.05 1.00 + 0.05 1.60 + 0.10 6.37 + 0.05 7.33 tt.42+ 0.05 + 0.05 4.50 + 0.10 2.31
DL-Gly2-

+ 0.04 1.00 + 0.08 1.58 !0.r2 6.37 7.r2+0.05 t 0.03 t 1.40 + 0.03 4.34 2.34!o.rc logF

+ 0.03 1.05 + 0.03 1.65 0.16 7.28+ + 0.06 8.15 + 0.03 13.12 + 0.03 6.46 + 0.08 4.36

D-Asnz-

voLH2 VOLH vo(LH)2

vol.
vo14H vot2
NO)2L2H-2

voI-2H_r

2.29t0.05 + 0.03 3.13 + 0.06 3.84 + 0.06 7.23 t 0.06 8.73 t2.64+0.03 t 0.07 5.36 t 0.06 3.31

+ 0.05 2.30 * 0.03 3.17 t 0.03 3.96 + 0.06 7.23 r 0.03 8.76 t2.64+0.03 r 0.06 5.36 + 0.04 3.29

r 0.05 2.00 0-04 2.51+

0.18 3.42+ t 8.06 0.06 t4.04 9.79 10.03 13.51 + 0.03 3.64

+ 0.05 2.00 2.42+0.07 + 0.09 3.40 + 0.10 8.01 9.32!0.04 i 0.03 13.59 + 0.05 3.55

The hieh stabilitv of the VOI4[Lr-VOI4(OH) of explained by tridentate equatorial coordination coordination an indiatio1 of. eguatorial. .o*pf*"it (a bind-ingof -s'ptwitrt the formation of iwo strongmetal cycles axiallequatorial of and groups Glu2- i tr"it Otton),whereas labitv of the of parameteil hu-r.r"*u", oneanda six-member The fieutiat. ;nJ;fthtl seven-member unstablean on forming of intbrmaon provide additional it "iu "p"Ole tri- these compleies The five-memberone' to-o" uaaition i" (seebelow). "i^rintit" structure li8and their of equatorialcoordinationof the first A1P2entate analysisof the stability.constants comparative A second a of addition the of for acids obstacles containing *itt otoOiu.e -amino to dis- coordinationcompounds ligandleads stereoof the sec-ond rgygals (Thble reliably l) #*:Th;-;t".d"nt "utiott ionngurations B-carboxy oiu"ttn"nt of the coordinated ^grouq.to.P ;J;;ti"tty on"lyfor the'formation of the VOtltt c-og Dyrneareconhrmed considerations xialposition.These otix witti a trientateligand (the aspartate)'The opttof constants attachment tt"p*ise i" trt" Jir "."i io yieldi a more stable complex tlan 'di;;t" by reversrble = This canbe explained togK$l o"i tf," racemate. Asp2- to Vo2+ and VoAsp: AlogK gr-oupot aminothe proton between the mieration of AlogKforbidentate rin:u"o ttte p-arboxygroupof AsP2-with altematfogr]!i =2J (Table1)' Indeed' polydentatecharacter of aliphatic amino acids.is as low as ini"utitution bf th" max-imum coordinaition below for the forthe in thti value Tutn G-s. This is demon6traled t7'--t.i friare r). imatl increase the with comPlex. (L-AsPH)VO(L-Asp) gk = l.8,Table l') is consistent *iotu-utl Clo o i,;;k ctituiion or iis y-carboxv group in voGlu' iJ ui"Oins of the additionalcarboxygroups.ofthe is con;; lig-;fi tu"ttion in theVoL2 complexes (see below)' lability nrmeiUy analyiisof their

proton relaxation coefficientsof -iotnit"*"t The molar with the composition oinuclea. are close. to zero ffOl+rnr{Vd;rtr1Op, thatthetwo indicates itti,r," < lb v(tot's)).'ihis

i{:t;Jie; ;;tt"*'

only spmexchaigeltTl' Thi: cannot antiferromagneuc shorten also magneticiloment, but i.Or"" itti e"ffective interaction' irt" "l.tifution time of t1e electron-nuclear exchanee spin Ull' fast ili;h is-;"ntiafv tn" ti-" of
RUSSIAN JOIJRNAL OF INORGANIC CHEMISTRY

to provide u'u',agng.Slgen

VoL 39

No,9

1994

1446

NAZVIUTDINOYA et al.

Thedriving force in this equilibrium is thefour-center iompetitin betweenth amino and p-carboxy sroupsfr bondingwith the protonandthecentralion' the ielative affinities of the aminogroupto the proton the sameas andtheoxovanadium(IV)areaproximately the in this case group.Note^that thoseof the p-carboxy and other each from aaaitionAfunctional lrups arefar "it iUlt no mutual repuhin. No sucha favorablevari"niof configurationispossiblefor the two ligandsof configuration. the opposite for exchange The rateconstants Ligand exchange. of ligandsL(k""-"') betweenthe solution bulk and the first coordination sphere of complexes VOL2 and of from thepH dependence werecalculated VOL4(OH) accuof the degree for found values the tl C;T2pusing (a). The calculationwas mutiioi of the complexes of the Swiftgenetalizatton a is on a relationthat based : 8] [1 Connickequations

in the glycineoxovanadiumflV)solutions concentration reacfor the exchange andthat theenopyof activation that the (-82 suggest J/(K mol) [10]) tion is negative proceed by a second-orderkinetic may ligandexChange route[2]. The high calculatedvalues of Kq1 for VOL2 and attention'They cannot VOI4(OH) (seeabove)deserve protons of axially the of be eiplained by relaxation groups, in because or hydroxy water mlecules bouncl thereis no spindensityof theelectron theaxialposition of the on the3d* orbitalin the neighborhood localized the only plane [16]. For VOL2 complexes, equatorial pdssibleexplanation is that the carboxygroup of the L oordinatedligand migratesbetweenthe axial and can positions. As a result,thelatterpositions eouatorial periodof time by watermolefor a certain b occupie cules.This lifetime is sufficientlylargefor the protons of water to relax in the equatorialposition and then with the Prgtg-ns undergoexchange from -thesolution scheme: following by the buk. This is illustrated

= T*'['*''*

(1)

PL,'

& !," 0 .,[L)-t ] +T r!* ,,

In equation (1), the first term in the par-entheses "ipr.it"t the'contributionto the relaxationfrom the "oiaiout"a protons of water o-r-hydroxygroups,39d of L; tft" i"o"a, from the protonsof the aminogroups p'-=plc*,'*here P iithe fractionof thecorresponding bound pitons, ty and T2y arc the lifetime and the time, iespectively, of thes-e rela,xatin -protonsin the Assuming that the water molecule in VOL2 spends In the calculametal. of the sphere fri coordination of thetime !r e-ach 50Vo P!$tign (eguatocontribution approximately (1), we assumed-zero equatioi tionsusing limit of therate the lower can estimate we rial andaxiali of ttr" ry)rLr(OA2complexes to the relaxation(see constantof boynd eqgato{ally an for exchange fioton to values (1) f above and the and kl"o equation parameters using the molec-ule water considered !* above)and K6gvalforVOL2 andVOIaH.Thecalculated coincide s-r-A similarestiof 1/ tff 2 Kon/PLs= G - 2) x 105 ForVO(Gly)2, s). V(mol to 2000 Aom iOOO uesranged also be obtainedfor VOLz(OH) VO(N;)2, VO(Val)2,and VO(Pro)2,the ?2v values mate of Vt$H can but in that caseit refersto the rateof proton werefound tobe 2.3 x 1'0{, 2-3x 104,3'9 x L0{, and complexes, equatoriallycoordinatedhy-droxygouPs in exch-ange As for the othercomplexes' 4.5 x l0{ s, respectively. ineversliblyprotonatedt the expenseof water moleof because to calculated be not could f of value the lt culesfrom the solutionbulk. (tpr ) T2v)'The caltheconditionof-"tlo* exchange" in forVOIa andVOte(OH)change Theftl"n values togetherwith the culatedvaluesof k|..0 are Presented the sameorderof ligandsL asfor CuL2:Cly- > Ala > datafor CuLz(takenfrom [19]) in Table2' Val- > Glu2- > Asp2-(Table 2). With respectto copto the firrnly estabA principal differenceof the resultsobtainedin this per(tr),this sequence colresponds snrv'fiom ttre earlier data for the oxovanadium(IV)- iirtrA uso"iative mechanism of ligand exchangeand is that Nagypalet aI.l4l andTomiyasu ieflects an increase to the attackofthe ;;'ir" system in the obstacles via ligandexchange takeintbcount not the abovelabilFor this reasq{I, Zi.ttoidid ligand 12,197. entering the that assumed They route. kinetic substitution ligand that the a r".nO-o.a"r dfinitlvindicates iw orde-r by a first-orderratecon- in oxovanadium(iV) via the proceeds reactionis described also -xchange complexes rH ttt" fact thatthe liriewidthof the NMR ;ffiiin in the kl*.n value The decrease mechanism. on the associative doesnot depend rig"i f* titglycine CH2-group
RUSSIANJoURNALoFINoRGANICCIIEMISTRYVoL3gNo.9|994

COMPLH( FORMATION AND LIGAND EXCHANGE

1447

Table 2. Rateconstantsforligandexchangeinsolutionsofaminoacidcomplexesofoxovanadium(Iv)andcoppers)[19 at at298K

s) /c!"0,V(mol
Ligand

voL2

vo[2H-1
(1.1t0.1)x107 (5.9+0.3)x106 (2.7+0.6)x106 ( S . Z t O S ) xt O 6 (4.4+0.5)x105

Culz
(3.310.2) x IU' ( 1 . 6 1 0 . 1x ) 107 (6.8+0.3)x106

GlvDL-ct-AlaD-ValDL-ValL-Pro DL-ProL-Glu2DL-Glu2D-AsP2DL-AsP2-

Gsto.t)xto7
(2.5+0.1)x107 (1.0t0.1)x107 (1.1t0.1)x107 (4.1t0.1)x107 (4.2+0.5)x107 (3.9+0.4)x106 (4.410.3)x 106 (3.2t0.2)xld (3.4t0.3)xld

(O.AtO.Z)xrO6 (2.9+0.3)x105 (5.0+0.4)x106

L ligands' is equatorial coordination of one o{ the > -VO(Val)2 > VO(Ala)2 for ' VO(Gly)z prgnounced alreadv is in thesequence ffect for solvation :;t;;;r,octing compfel thg gnte{rnS conditions the of hydrgly d ;;il;i;rigratign 9" ligand the bis-aspartate the attacking

positiondoesnot noticeably andby growthot tr.tttUttacles to eroupinto the equato'rial withanincreasernthevolumegfthesidealiphatic lrbility'of vO(Asp)z(oH)3-comparedwith which contains il'tt prolinate' for that, seem might ;dJt of of VO(Asp)f,. The effectsof differentconfigurations nitrogen'-ai* i'n tt't ring' the effect a secondary is balof the complexes hrge; however',this stt-ourJe *tioo acison the lability parameters ;r*;ffi"rei of the limits of character) within fall .ooJtt b;i"itv iuieophilic ;d;-"-th; stability #; ililsh;t of which the experimental asa-ps-ult errors. thePro- nitrogenatom(seeabove), in tulI labile' of oxoin solutions ut*oslequallv ut" reactions Thus.lieandexchange lrVicrvi, associative an mechanism' bv proceed exchange the associative "*;'ilil(ift*fr"i.t *.j*ia comfor copper(tr) simitatiothaticnown ;"&il the valine' and carcr-alanine' ligand glycine, the Note that, for ifievet, the fast migration of ;dpositions coraxialandgqTtorial thal for the boxv sroupsbetweenthe k]*.0 valuefor VOL2 is slightly larger as un{eJinvestigation' svstem tn" oxothat fact the ;;;6;"*"oln despite rffinding CuL2complexes, oxoof position a'single of for "if * ttt" existence -axial hasa singleaxial pbsitionaccessible vanadium(W) featursof the mechaspecic in such two ;;;darvj,-result ttre of. initead ;;hJtttitg-iie*d fact is nism of ligand substitutionin its complexes' nris remarkable

ffiilii ;i;

copper(u)-n' of dissociation easv vif," u6u"-tn"ntioned

ACKNOWLEDGMENTS thebondbetweenoxovanadium(w)andthecarboxy of the attack"o "TL. fni, u.."i"tut"t displcement wascarriedout with financialsupThe investigation *ia positin to the equatorialone f li;iffitrtt for Fundamental the otherhand' poi'ito* tttJnossi-Foundation in the limiting stageoiitt t"actign' gn M' 93-03-57 no. ffi;fii-;J fositionbv theadditional fr"atctt, Project tffi VO(Glu)l- and carboxygroupsof the ligand in the REFERENCES makesthem less labile compyVazdgysVO(Asp)l- complexes 1. ^ Yaaimirsk,K.8., Kriss,-E'E'. and MetKomplelcsw Ustoichiuosti paredtothecorrespondingcopper(tr)comporrrtds,in Konsiaity k";",vt, "-';;;;f blocking The free' pition iemains iib1ki*iisLtiitvCon't'nt'oTMetalcom1979' Dur.ka" which is ilU1; t";'b, ri"u' Naukova ;it""g for the aspartate' ;tp*i^uy ;; ;i#xexes This (seeabove)' A.V. and Shtyrlin' V'N". Bystryz Reak of strongtnntaUonding 2. - Vay,harov, capable Reactions)' ffast'Ligand-Exchange Tu*r'tii*ta* than tenfold reducesthe lability of VO(Asp)l- more Univ', 1985' f'*^t Kazan. for kl'o of vahre lower Gordon,G" J' Coord' Chern" 1973' The and H. Tomiyasu, Cu(Asp)l-' to 3. with respect of the vol.3,no.I,P.47' VOI,(OiH) than for VOLa is also an indication Acta' 1982' the of i'e'' Nagypal,I. and Fabian,I" Inorg' Chim' 4. complexes' in VOL2(H; ;id't;iing 193' vol,'62,no.2, P. and axialequatorialcoJrdinationof tn"it OH- group
CHEMISTRY RUSSIAN JOURNAL oF INORGANIC VoL 39 No' 9 1994

tM8

NAZIvIUTDINOVA er al'

of Metal-Ion C2rnplqes' Part A: "' Stabiliry Constants 't2. E' Ed" oxford: Perganton' 1irhg*d",H6gfelat, 1982. Gillard' R'D'' A'N', andDg]yatov'F V'' P^oliyL'F'-and Boas' Yu.I.,Glebov, Vilas nikov, J', Sal' 1 "' 3. Pessoa, O. Cortu "' (PolynuclearComrr13' v'Rastvtorakh e'P' no' 8, xoipi"ntv ;;; F;i;tre;;;,1sss,vol' univ'' 1989' Kazan' S;ilf"ntj, Ku,*' ;;ir J', Vilas Boas' L'F'-and Gillard' R'D" A'V.' et al" 7. '' CostaPessoa, Zakhatorr' Ya-E.,Shtyrlin,V'N'' A. Zfl' aerntan, * 9,no't7'p'2t01' 388' Fiyar"i1sgo,vol' 2' no' 37, P' .i;;;;'Kht*',tggz,vol' A' 1969' R'l-" Vlfs Boas'L'F" et al'' J., Mar,ques' 8. CostaPessoa, Childs,C.W. -a Perrin,D'D" J' ChemSoc' 15. p' or' I' no' 9, vol' 1039. Polyhedron,1990' no.7, P. et al'' 16. Ballhausen, C.J. and Gray, H'8" Inorg' Chem" 1962' J'A''-VilasBoas'L'F, Antunes' J., Pessoa, 9. ' Costa 3' p' 414' no' 21 vol.1,no.L,P.37. i."ire. Eintem',L99l'vol' 43' K', ?4 Gordon'G''Inorg' Chem'' 17.Carlin,R.L-,Magnetochemistry'Heidelberg:Springer' H., Dreyer, 10. --' Tomiyasu, 1986. 10, no' P' 2409' lgi uot' IL, Phys'' t962' 18. Swift, T.J. and Connick,R'E" J' Chem' Analiza Metod ' 11. "' Popel',A.A-, Magnino'Relnluatsionnyi Relaxation vol.3'l,no.2,P-307 et al" ri[iiiil irri ininun fY"el"F '- Sityrlin, V.G.,l'berman,Ya'E" Za\nto1.'A'Y" Mos- 19. Substances)' 27'no'9'p'2291' vol' Methodfor tneanalysisof notgni" Kiim-,1982, zifrs. cow:KhimiYa,1978'

etal" LF' gitlTd' R''D" Boas' J',Vilas Pessoa, 5. Costa "' 1245' t4'P' F;i;;;i;,1ssb, nol 7,no'

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