ELSEVIER

lnorganica Chimica Acta 279 (1998) 24-29

Syntheses and X-ray crystal structures of cis- [ Mn (bipy) 2C12]- 2H20" EtOH and cis- [ Mn (phen) 2C12] ( bipy -- 2,2'-bipyddine; phen = 1,10-phenanthroline); catalysts for the disproportionation of hydrogen peroxide
Sebastian McCann a Malachy McCann ~'*, Rev. Michael T. Casey a, Maura Jackman b Michael Devereux ~', Vickie McKee ~
"Chemist~' Departme~t. St. Patrick's College. Maynooth, Co. l~'ildare, Ireland b Dublin Institute of Technology. Cathal Brugha Street. Dublin. Ireland "School of Chemisto,. Queen's Unitwrsio: Belfast, B19 SAG, UK
Received 20 May 1997. received in revi~d form 24 June 1997. accepted 25 November 1997

Abstract

MnCI~.4H:O reacts with 2,2'-bipyridine (bipy) to give cis-[Mn(bipy)2Cl:! (I), and recrystalli~tion of I from ethanol gives cis. [Mn(bipy)~Cl:] .2H~O.EtOH (2). MnCI:.4H~O and l.lO-phenanthroline (phen) react to form cis-[Mn(phen)~Cl~l (3). in each case, the X-ray crystal structures of 2 and 3 show the mangane~(ll) atom to have a similar distorted octahedral geometry, and in both cases t ~ is extended ~=~ stacking of the conjugated ring systems. Compared with MnCl~.4H~,O, I and 3 are much more efficient catalysts for the dtsproportionation of hydrogen peroxide. The catalytically active species are I~lleved to be IMn(hipy)~(it~O),l ~' and [Mn(phen)~(H~O)~] ~* , respectively. 1~8 ElsevierScience S.A. All rights reserved.
Ke)~,ord.v: Cfy~t~l ~fulur~;Ma.~.ne~c omple~~; Bipyfldlne omple~e~; Phenanlh~li~ ,~mplcx~,~:Calalyti~:di,~p~)p.flionatioa

I. Introduction

A number of manganese~containing non-haem catala~ have recenOy been isolated and charactedsed II-31, and these cataly~ the disproportionation of hydrogen peroxide, a reaction which is important for cell detoxification: 2H~O~~*O~ + 2H~O Presently, there is a lot of interest in preparing and charactedsing biomimetic manganocnzyme complexes in order that the mode of action of the natural catalases can be established [ 4-12 ], Recently, we have been engaged in the synthesis and structural charactcrisation of mangane~(ll) carboxylate complexes [ i~211 end, in particular, complexes containing dicafl~oxylic acid ligands [ 17-21 ], A pz-ct~;u;n~-y~>~c.-.~,ment of the ability of the complexes to work as functional biomimics for m a n g a ~ catala~s showed that dicarboxylate complexes, containing the ancillary chelating NN donor
C ~ ~ aurar,Tel,:+ 333-I-'7083767: fax: +353-I-708 3815;

ligand I, 10-phcnanthrolin~, (phen) I 17-201. wt:t~ particularly active catalysts for the disptopottionation of hydrogen peroxide. Conductivity measurements, taken on aqueous solutions ot the phenanthroline-carboxylate complexes, sag. gested that there was extensive dissociation of the complexes in water with consequent formation of [Mn(phen)~(HaO) a I: *, Thus, it appears likely that it is this dication that is primarily responsible for the catalytic breakdown of peroxide by these model complexes, although the nature of the de-coordinated free carboxylate anions also appears to influence the rate of peroxide decomposition. As an aid to our understanding of the reactivity of the carboxylate-phen. anthroline complexes, we have now synthesised and characterised mangane~(ll) chloride complexes containing the NN donor ligands 2,2'-bipyridyl (bipy) and I,lO-phenanthroline, and investigated their catalytic activity towards peroxide,

:2. Exl~dmental
Chemicals were purchased from commercial sources and used without further purification. Infrared spectra were

):,~I~M~t$ - ~ fret r~r I~ Ptt $ 0 0 2 0 - 1 6 9 3 ( 9 ~ )00031-0

Elsevier S~i~nce S,A, All rights rc~rved.

S. ~ c f o n n el al. / Inorgank'a f h i m i c a A(,ta 279 (t998) 24-29

25

recorded as KBr discs in the region 4000-400 cm- ~ on a Nicolet Impact 400D F r - | R Spectrometer. Magnetic susceptibility measurements were made at room temperature using a Johnson Matthey Magnetic Susceptibility Balance and conductivity measurements were taken at 25(: using an AGB Scientific Ltd. model 10 conductivity meter. Elemental analyses were carried out by the Microanalyticai Laboratory, University College Cork, Ireland.

oi'bserved. The data were corrected for Lorentz and polarisation effects and empirical absorption corrections were applied.

2.3. Structure analysis and refinement

The structures were solved by direct methods (TREF [221 ) and refined by full matrix least-squares on F-', using all the reflections. All non-hydrogen atoms were refined with anisotropic atomic displacement parameters and hydrogen atoms, bonded to the carbon atoms of bipyridine or phenanthroline, were inserted at calculated positions with isotropic displacement parameters riding on U u of their carrier atoms. in the case of cis-lMn(bipy):Cl.,] .2H,O.EtOH (2), the hydrogen atoms on the solvate water molecules were located from difference maps and not further refined; those of the disordered, partial occupancy ethanol solvate were not included. All programs used in the structure refinement are contained in the SHELXL-93 package 123 I.

2. I. Co, sial data

Crystal data for cis- [ Mn (bipy),Cl: 1.2H, O. EtOH (2) and cis-[ Mn(phen)_,CI.,.! (3) are summarised in Table I.

2.2. Dam collection and l)rocessing

Both data sets were collected on a Siemens P4 diffractometer using graphite monochromated Mo Kct radiation. Unit cell parameters were determined by non-linear least-squares refinement of 33 reflections ( 10 < 20 < 25): crystal stability was monitored by recording 3 check reflections every I00 reflections, and no significant intensity changes were
Table I Crystal data

2.3.1. ('is-lMn(bi:)y),Cl,.l !) To a solution of 2,2'-bipyridine (0.984 g. 6.3 mmol) in ethanol (30 cm a) was added MnCI,.4H,O (0.5 g, 2.527

cL~'-IMn( bipy ) :(?1~ I ' 2 Ho,O. EtOH ( 2 )

('i~-I Mn( phen ),CI: I (31 C..sH,,,CI~MnN,~ .IX(), 25 yellow block 15 ~l 2 ) I)7107J
illoiit~:liili t).4~l)ll(II) )

i].ml'firical h)rnmia Poriillllii weight C~,~tlil dl;scription Teml~riitnre ( K ) Wilvelenllih I ~ )

('iy~lill <~),~leii! ~lliit.'e ~rl!lll! o I ~ll )

C~.FI=,~CI:MrIN~O, 41)3.26 yellmv iihick 153( 2 ) 0.71073

nlilnllc, lhii ( . / ,. Ill, lOll(l) )

biA!
c (A I ~t (1 V (~) Z
[ ~ n x i t y Icalcnhlted, iti ( n l n l i )

13JJ21J) I I ,.t24( 6 ) 123,(~4( 41 24l)1 ( 2 ) 4

I~ Iql12) 14,J5412 ) 914,62( I t 2(),'I I, I( 4 I 4

I,St)O 0,934

Mg lit

~)

1,3{14
0.799

b'(OfiO ) i~stiil size ( mm) 0 riilllle I'or diitll collection I )

Index r a n g e s

I016 ().625 X 0.325 x l).275 2.36 to 25.00

0 < h < 22 -I<k<15 13</< I I

~Jl414 0.42 0.214 ,,<O, 18 5 2, I 0 to 25.1X)

- 0 < h < II

-I<k<18 - 17<1< 16

Reflectionscollected
Independent reflections Absorption correction Max. and min. lransmissiorl Relinelnerlt method Dalalrestraintslparanielers Goodnessoofolit on F: Final R indices I I > 2~r(i) i
R indices ( all dillq )

2370
2113 t R,,,, = O.OI 7 t) ) semioempirical { I~/-SCiillS) 0.92~ aild 0.1,186 fullmatrix least-squares on I": 2113/0/142 1.089 Ri ~ ().0431) ll'R2 ~ O. IO t) I
Ri = 0.I).5()5

40314 3555 ( R.,, ~ (i,03214 I ~emi-cnlpirical ( i/v~clin~ ) 0.I,I04 avld 0345 full-niatrix Icasl-squan.'5 (m if.': 3555/0/280 !.027 Ri ~ 1),(15,18

u'R, = O. 1252

R, = 0.()925

wR2 = O. 1141
Largest diff. peak alid hole (e A~ ' ) 0.975 lilld -- 0.597

wR2 = O. 1458
0.670 and - 0.643

2'~

S. McCann el al. /Inorganica Chimica Acta 279 (1998) 24 29

retool) and the mixture was warmed gently and stirred for 0.$ h, "rite precipi~ted yellow product was filtered off and the filtrate was concentrated by rotary evaporation to give more of the yellow solid. The combined solids were washed with two small portions of ethanol and then dried in vacuo. Yield: 0.75 g (68%). Anal. Calc.: C, 54.8; H, 3.7: N, 12.8. Found: C, 54.6: H. 3.7; N, 12.1%. IR: 3060, 1600, 1490, 1440, 1315, 1245, 1150, I!00, 1060, 1020, 820, 775, 735, 650. 625 cm-~./.t~,-r=6.17 BM (20.7C). AM(H20)= 2Y--; S cm" tool- t. The complex was soluble in water, methanol and ethanol, and insoluble in chloroform and ethyl acetate. Recrystallisation of the .solid from ethanol gave crystals of form ula cis- [ M n ( bipy ) ,C l, 1.2H,,O. EtOH ( 2 ) which were suitable for X-ray analysis, 2.3.2. cis-IMn(phen):Cl:l (3) To a solution of I. ! 0-phenanthroline ( I, 139 g, 6.32 mmol) in methanol ( ! 5 cm ~) was added a solution of MnCI2.4H,O (0.5 g. 2.53 retool) in methanol ( lO cm~). The resulting yellow suspension was stirred for 0.5 h at room temperature. The yellow solid was filtered off, washed with three small portions of methanol and then dried in vacuo. Yield: !.0 g (gi%).Amd. Calc.: C. 59.3. H. 3.3: N, ! 1.5. Found: C, 59.1: H. 3.3; N. ! 1.3%. IR: 3050. 1620, 1580, 1515. 1430, 1345, 1220, I 145, I 100, 845. 780, 730, 640 cm = ~. #~,= 5.84 BM (20.3C), Am(H~O) ~ 202 S era: reel ~. The complex was soluble in water, methanol and ethanol, and insoluble in chlorolbnB and ethyl acetate. Recryslallisation of the solid I~om methanol gave crystals of 3 which were suitable for Xoray analysis, 3, 4, ilyd~,,~,en per~,,tide di,~'lu'vporth..ai~ m ,~tmti,' Aqueous H~O~ (35t~ wt,/wt,, 30 cm ~. 342 retool) was ~dded to a solid mixture comprising the complex ( ( I ) IO, I rag, 2,07 10 :s reel; (3) 10,5 rag. ~.,39 10 reel: I0,1 rag, ~,10 l0 =~' reel MnCI=,.4H~O) and imidazole (lO0 rag). The combination was stirred and thennostalted at 25C. The evolved O: was measured volumetrically.

C1

CIo

C9

C1 C8

C3

C~

Fig, !. Structure of cis- I Mn(bipy ) 2CI, I" 21t,O- EtOH (2) ( water and ethanol molecules omiued for clarity ). Table 2 Seleclcd bond lengths ( A ) and angles ('~) for 2 Mn~N( 2 ) Mn=N( I ) Mn=C! N(2)'=Mn~N(2} N(2)'=Mn~N( I1 N( 2 )~Mn~N(I) N( I )=MB=N( I )' N( 2 )'=M.~=CI N( 21 =Mn~"l N( I )=Mn=('l N( I )',,=M.:CI 2,2?5( 3 ) ,,..=' '~87( ~ .~) 2.4834( II ) 162.6t~( 13} 95,31(I0) 71,93( lot ~7,61(14) ~)8,18( 7 I ~).~,77( 7 Ih~5,h 7 t ~1 ,(d!( ~

3, Results and dbcu,~ion MnCI:,4H:O reacted with 2,2'-bipyridine to give Ihe yellow solid ci,~'qMn(bipy)~Cl:] (1) in g~od yield, and ~rystallitatkm of I from ethanol gave crystals of c/sIMn~,bipy)~CI~I,2H,O,EtOH (2). The reaction of MnCI=,,4H~O with I, I(bphenanthroline produced the yellow c~m~plex c/s-|Mnqphen)~Cl=,] (3), The preparations of I [ 241 and 31251 have been reported previously using similar synthetic strategies,

The Xoruy crystal structures o1'1 ~ ( Figs. I and 2) and 3 (Figs, 3 and 4) were obtained and are discussed togetl)er ~low. Selected bond leng|hs and angles for 2 and 3 are listed in Tables 2 and 3, respectively, in each structure, the man ganese atom is six-coordinme but the geometD~is far removed lh~m ~|ahedral, principally due to the 'hilC of the bipyridine and phenanthmline ligands, The manganese ion in cis. I Mn(bipy),Cl~ I' 2H,O. EIOH (:2) sits on a twodbld axis, whereas cis, I Mn(phen) ~Cl~I (3) has no internal crystallo graphic symmetry, In spite of this, the geometries of the two complexes are very similar (see superimposed piclure~ in Fig, 5), There are small difG.,rences in the tilt ~,!"the planes of the conjugated iigands, which c:~:~probably be accounted for by packing interactions, la both cases, there is extended
The .~l~ture of the cL~-I Mn(bipy ~:CI, I i~Mion of cis-I Mn( bipy )~ CI:I,?.H:O, EIOH (2~ q,~pacc group C2/('~ is basically the ~amc as that I~Viously ~l~Hed by Lumn~ ~md Lindcll 12(~1 Ior ('e.solMn( hipy L,CI: I (Sl~aCe group P2~ lc), ~though there are some differences in the specified bond lengths and angles qe,g, CI-Mn-CI an~,le in 2 is 92,72 <~widis~ for the Lumn~: and Lindell structure it was 100,75).

$, McCmm el a/, / bu~rgm~ica Clffmh'~l A~'tr~ 279 i ~'~'~,~)2,./-29

2?

Fig, 2, ~r~r slackingof the conjugatedring systemsin 2. 'ire'n" stalcking of the conjugated ring systems, characterised by the inteq~lanar distances ill1the i'~|nge 3,3o~3.5/A ( see stacking plots in Figs. 2 and 4). There is no solvent in the hlttice o1' ~'iso J M ~11phell ) ~CI~J (3) but the ilsymmetric unit o1' riso J MII( bipy )fl?l~ I ' 2ii,O. EIOH (2) t'ont{lins a Wlltel' mole,o

cule and a half-occupancy ethanol molecule (disordered about a two-fohl axis). The etha!lol and water arc hydrogenbonded (Olw-O21 2.775(8) A). Furthermore. the water molecule also interacts w!th the chloride ligands (Olw-CI 3.293(3) and 3.258(3) A) under transformations (of the Ci) x, - y , i/2 + - and x, y, I + :, respectively. Aqueous solutions of ris-I Mn(bipy):Cl:l ( 1 ) and ('is I Mn( phen )~CI~ I (3) were highly conductive. This implied that there was extensive dissociation of the chloride iigands tlpon dissolution of the complexes in water and consequent fl~rmation of the respective dications IMn(bipy)~o ( t1~O)~ I~' and J Mn( phen)~( H,O)~ I : ' Although corn i'~lexes I and 3, by them~elve.~, were quite illel'fectiv for the dispropt)rtionation of t1~O,, they hoth vigt~rously cataly,~ed the breakdown o1' the peroxide in the i')re.,,ellcof ~dded imid ~ a/olc ( Fig. (~), It should bc noted that the imidaz()lc I~l,,,c by

1
Fig. 4. "n'-'rr slacking o1"the c,mjugated ring systcm~ in 3.

S. Mcf.~mn et aLI Inor,g~nica Chimica Acta 279 (1998) 24-29

Table 3 Selecled bond lengths t/k) and angles () for 3

3000
eq

IMn(phenhChl IMn(bipyhClJ

Mn-N(2A) Mn-N{ lB ) Mn-N( 2B )

Mn-N(IA)
Mn..CI{ l )

2.281(4) 2.299(4) 2.341(4) 2.371(4) 2.4396(14)

"-" 2500
2000 >
a

1500
MnCIz.4H20
~ qm~ ~ mm m

Mn-CI(2)
N( 2A)-Mn--N( IB ? N(2A)-M,PN(2B) N(IB)-Mn-N(2B) N(2A)-Mn--N(IA) N( IB)-Mn-N(IA) N(2B)~M~N(IA) N(2A)-Mn-.Cl( I) N( IB)-Mn--CI( 1) N(2B),-Mw4~I( 1) N{ IA)-Mn~CI( l ) N( 2A)-Mn,-CI(2) N( l B)~Mn.~'I(J) N( 2B)--Mn-4~I(2) N( IA)=Mn.-CI(2) el( I )=Mn=Ci(2)

2.4544(13)
159.10(14) 88.93(14)

1ooo
~

lemagm

mm

(~"

500 0 o 2 4 6 8 10

71.63(14)
71.28(13)

97.88(13)
82.43(13) [02.91(10) 94.11( l I ) 160.93(10) 87.24(10) 90,63(9) 97.00(10) 90.59{ 16) 160.63(10) 103.99( 5 )

time (rain)

Fig. 6. Kineticcurvesfor the catalyticdisproponionationof hydrogenperoxide by cis-[Mn(bipy)~Cl~l (I), cis-lMn(phen)~CI, I (3) and MnCIo,, 4H,O, in the pte~nce of imidazole,

.J

j'

,,d

Fig, ~, Structures2 an~ 3 s u p e f i m ~ omitted forcl~tly),

(waterand ethanolmol~ulesof 2

i t , l l causes only a very slight disproportionation of peroxide and that this sluggish reaction is greatly enhanced when the mangane.~(Ii) complexes I and 3are included in the reaction mixture. Such an enhancement in the rate of peroxide disproportionation in the p ~ n c e of added base has also been reported by other worke~ 18.9,12,2T ! and, significanOy, betn3cyclic bases ate known to be present in the vicinity of the active sites of manganoenzymes 128 ]. The number of H:O~ molecules broken down by each manganese atom, in complexes I and 3, during the first minute of the reaction was es~ntially the same (5322 and 5382,

respectively) 2 After 25 min, about 75% of the peroxide had been converted to O:. After a reaction time of i.5 h. about 90% of the peroxide had disproportionated and this implied that any side reactions involved in the consumption of H.~O2 molecHes were insignificant. In contrast, under the same experimental conditions, the simple manganese(ll) salt MnCI~. 4H20 was found to be considerably less active than I and 3 as a disproportionation catalyst (9 i 8 H,O, molecules broken down by each manganese atom during the first minute). These resulL~ substantiate earlier findings 1131 which showed that maximum catalytic activity towards peroxide occurs when the concentration of 'free' manganese ions is minimi.~d, i.e. when the metal is ligated by bipyridyl and phenanthroline. Furthermo~, a brown suspension of intln ~anese oxide was noted to Ibrm during the MnCh.4H~O catalysed reaction, whereas with catalysts I and 3 the reaction solution remained essentially colourless or pale yellow both durln8 and after the reaction with peroxide. Thus, it is evident that the presence of bidentate chelating NN donor ligands, such as 2,2'-bipyridine and I, 10-phenanthroline, in the coordination sphere of the metal aot only significantly enhances the ability of the manganese to disproportionate H:O.~ but aiso inhibits the formation of insoluble manganese oxide. These results corroborate our other findings from catalytic studies on a number of manganese(li) dicarboxylate complexes. Finally, cis~lMn(bipy).,Cl, l (I) has previously [301 been used as a catalyst for the liquid-phase oxidation of iso. propylbenzene by molecular oxygen, indicating the additional potential ,scope for this and related manganese(ll) reagents in organic synthesis.
~'It was previously established 1291 that Ihe &'composition of hydrogen peroxide (0, I M ~ueous ,solution) by cis. [ Mn(bipy ).,CI~] ( I } is zeroorder and, at pH 7,09, the rate constant k was (1,35:i:0,02) x iO~ mole H~O., rnin ~ ~,The overall rate constant was calculated from the kinetic curve and referred to one mole of hydrogen peroxide decomposed by one mole of

catalystper minute.The pre~nt disproportionationstudieswerecarriedout witha muchhigherconcentrationof hydrogenperoxide ( I 1.6M) and also in the presenceof the helerocyclic base iraid~ole.

S, McCann el al, / Inorganica Chimica Acta 279 1998) 24-29

29

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1171 M.T, Casey, M, McCann, M. Devereux, M. Cuwan, C. C'ardin, M, Convery, V. Quillet, C. Harding, J, Chem. Soc., Chem. Commun. ( ! 994) 2643. {181 M. McCann, M.T, Casey, M. Devereux, M, Curran, V. McKee. Polyhedron 16 (1997) 2741. [19l M. McCann, M.T. Casey, M. Devereux, M. Curran, G. Ferguson, Polyhedron 16 (1997) 2547. [20] S. McCann, M. McCann, M.T. Casey, M. Devereux, V. McKee, Polyhedron 24 (1997) 4247. [2 !] M. McCann, M.T. Casey, M. Devereux. M. Curran, C. Cardin. A. Todd, Polyhedron 15 (1996) 2117. [22] G.M. Sheldrick. SHELEXS-86, Acta Crystallogr., Sect. A 46 (1990) 467. [23 ] G.M. Sheldrick, SHELEXL-93, University of Gi~ningen, Germany, 1993. 124l K. Yamasaki, Bull. Chem. Soc. Jpn. 13 (1938) 538. 125 ] R.D. Dowsing, J.F. Gibson, M. Goodgame. P.J. Hayward. J. Chem. Soc. A. (1970) 1133: R.E. Morrison. C.F. Bell. J. lnorg. Nucl. Chem. 35 (1974) 1865. 1261 P.O. Lumme, E. Lindell, Acta Crystallogr., Sect. C 44 (1988) 463. 1271 P.N. Balasubramanian, E.S. Schmidt, T.C. Bruice, J. Am. Chem. Soc. 109 (1987) 7865. 1281 E.J. Larson, V.L. Pecoraro, in V.L. Pecoraro ( ed. ), Manganese Redox Enzymes. VCH, New York, 1992, Ch. I, and Refs. therein. 1291 A.Ya. Sychev, Ya.D. Tiginyanu. Yu.S. Gromovoi, Russ. J. Phys. Chem. (Engi. Transl.) 42 (1968) 1097. and Refs. therein. 1301 A.Ya. Sychev, I.M. Reibel. L.P. Podgomaya. Russ. J. Phys. Chem. (Engl. Transl.) 43 (1969) 370.