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Synthesis and characterization of molybdenum(II) and molybdenum(V) monothiocarbamate complexes. Crystal and molecular structures of tetrakis(isopropylmonothiocarbamato)dimolybdenum(II) and oxobis[di(oxoisopropylmonothiocarbamato)molybdenum(V)]
ELSEVIER
InlwganJea ('him)ca Acia 2{~7 I Iqt)HI 11)1-11)7
Synthesis and characterization of molybdenum(II) and molybdenum(V) monothiocarbamate complexes. Crystal and molecular structures of tetrakis (isopropylmonothiocarbamato) dimolybdenum ( II ) and oxobis [ di( oxoisopropylmonothiocarbamato )molybdenum(V) ] Anthony D. Calcaterra, Scott B. Kimble, T.L. Groy *, T.M. Brown * Ih'parltll¢lll o/{'h¢itil.~tl:v t/lid II.ichemi.Wrx, /hll ,~71 filM, Arizona .~t.ll' UmrerJitv, Tempe. AZ ,~52,~7.1604. 1/571
Reg.'tired 2~ N~l~,:eillher ItY~fi: accepted J March I*)t)7
Alistrllet The compound Mo.( SOCNR: )= ( R = i-Pr ) has heen prepared from the reaetitm of a ,m)ichit)n)ctlt=." ~llllOt,lllt of lithium monothit~arbamate will) M o : l O,('CI~I ~).= in ¢ihluiol, The con)pound was then reacled willl molecular o,xygcil Io fornl the (~xidized product M o : O , ( S O C N R : ).=.
The strtiettll'e of the isopropyl derivative l~tir'i|.~i+btained US)hi sinllc-¢ry.~ial X-ray analy.~i.~. Moq SOCN< ioPr): )+. 2THF crystallizes in the Irit'lini¢ .~llat'e gl'~mp PJ wilh Z + I :uid unit call diln~llsions +l = 1l).3tJ61"il A. h= 11.473(3) A. (.= 11.7791 3) A. (i + 751)312)'. = 1(M.34( 2 i <~,? = 114.2712 )" and V = 12'~I.=l( 51 A '. Crysiallogi'al+hic sitidie~ lia+e also b~cn conipleled fiw the MoX).I S()CN( i-Pr i: I, ¢Olltplex. which t'l')sttillitcs ill Ilic orlhoihiiinliit: sp:l~e +i'
I, |ntrodl|etiou The most recugnized t)l the letrllkis(carl'~oxyhllo)dirnt)lyhdcnum(ll) compounds will) Mo=M,~ quadruple honds is letraki.~(acelato)diniolyhdenul)l 11.21. Mo:=
(O~CCFI~)<~. The diamagnetism of the carboxylates alotlg with a significantly shod Mo-Mo distance indicate~ a direct metal=metal interaction. In order |o satiM'y the 18 electron rule, a quadruple bond is fornl)dated to exist between the metal atoms. The ease of replacement of the carboxyl,'de groups, the high unsaturability due to the qtmdruple bond and tile low oxidlllion stale of tile metal all cotitrJbute to the fact that these species have become excellent precursors for further reactions. ]'he number of compounds containing lhe M o ; = ' n)oiety, with a quadruple bond. isquite lengthy, showing a diverse range of coordiu;ttiOll with both monodenlate mid bridging bidenlale ligands. The replacement of tile acetales with uuivalenl bideiitate ligands, such a,, xanlhales ( S z C O R ) . dithiocarl)amates (SzCNR..,), dilhiocarboxylares ( S , C R ) and nionothiocarboxyhites ( S O C R ) , were ~ CorreMxmding auuhtw~,.Tel.: + I 6[)? t~l"~53461: fax: + I 602 (~()5Fl6()7. (X)20-1693/98/$10.n0 (¢~ It)08 F.l,,,.eVJ¢l,Science S.A. All rigllt~, rosen'veal PIISO020- 1 0 9 3 ( q 7 )05561 -8
initially investigated in the early 1~7() ,, 13'~l. TIw major eil|lllta~i,., was to Jilve,',,lJ~lt¢' w h l l l cf'iccl tilL' rel')lilCL'lilelll ol i~("(), by R(]S, or R(TS(:) nlighl have Oll the I))¢'tal-loo metal holtdillg, and if, in filet, these i1¢w ¢OlllpOllnd~ wonld retain ihe JlIIIJLII "il¢~lill~,,lyrl~' strlll21Lir~ or possibly uudcrgo an oxidativeoaddilion reaction, as discovered by Wei~,s and co-worl~ers J61 it) 1()72. A less frequently ¢ll¢Ounlered ligand, monmhio¢:lrbamate ( S O C N R , ) , is a univalcnl hidentate ligand oh'selF related Io the wellocharaeterized dithioearb:mlale ligand. Monothioqarbamate ¢omplexe,, h:l,~c been prepared only since the early IqT0s, with ;lltentilm ten lered primarily on the litter transition mctab,, it was therel'or¢ o1' interest to investigate the reaction of M o : ( ( ) ~ C C H , ) ~with the litllium isol:~ropyhlionothiocarbamale .salt to determine if Ihe proposed compound. Mo.:,( SOCN( i-Pr ): I~. would main° lain the original acel;.lle slructure or p¢)ssibly undergo the oxidative-addition reaction similar to the dithiaearbamate work of Weiss and co-workers 16 I. The isopropylmonolhiocarbarnale derivative when reacted with molecular oxygen forms a con)pound having the ;ormula M o : O , ( S O C N ( i Pr):).~. The structural properties of this compound were ab, o urMer invesligation.
102
AD. Cah'aterr, et ld. / Inor~amcaChimwaActa267 f l!~8J 101-107
2. Experimental 2.1. Preparatitm t!l'mot~t,thiocarbanmte ligand lithiun~ N.N.dii.~opropyhnonothiocarbamate. Li( SOCN( i-Pr),_) This particular ligand cannot be purchased commercially, unlike the ditl:l~ca~amate analog. The monothiocarbamate ligand was prepared according to the method of Hawthorne et al. [ 101. 2.2. Preparathm ¢~'molylnlemt,1 acetate dimer: tetrakisl carl~m'htto Jdimolyhdemun( ll ). Mo :( O :C CH d ~ M,olybdeaum{ I!) acetate was prepared by the literature ntethM of Brignole and Cotton ! ! I !.
2.3. Synthesis of Mo:tSOCNfi.Pr):)4 Mo:( O=,CCHj ) ~ ( 0.65 g. 1.5 mmol) and LiSOCNI i-Pr), t l.01 g, 6.! mmol) were loaded into an extraction vessel. The vessel was outgassed and approximately 50 ml ofethanol were vacuum distilled onto the reactants. Stirring the solution tbr alx)ut 12 h pr~xiuced a dark red solution, The mixture ,~parated into a dark greenishobrown solulion with an insol. able red powder .~ttling to the bottom. The solution was decanted to the other ~ide of the vessel. The solveltt was distilled back onto the original red powder leaving a dark greenish-brown residue behind, This process wa,,, cominucd tmtil the sohlltnll tlbOVe the solid pl~tict was relatively colorles.~', three or four eXtl'actioli~ Wel'¢ '~tifttciellt, Ethanol should not he leli on the product tier long periods a~ uiid~.,sh-. able l~Olll~OUtld% l a y I'orm or cause dccollll~i,dlion of Ih¢ desild i,toitl~nd, The ~ihlinol was removed and tile vessel was l i m l ~ d in v,,ioJo for approximately 12 h. The vessel was brought into the glove I~lx and the Mo:( S ~ N i i-Pri: i, wits stored in a ,,~rew cap vial, Yield 0.82 g. 65¢~,, Anal. Cute.: C, 44.26; H, %38; N, 5.74', S, 13, i I. Found: C, 44.25; it, 7.58: N, 5,74: S, 13,54~'~-.
3. Structure determination 3.1. Single-co'sml X-ray studies 3. I.I. General The diffractometer setup used for all single-crystal X-ray studies was a Siemens P3. The diffractometer was interfaced with a microvax 2000 computer, containing all the required software to collect and process the data and to solve the structure. The structure was solvc~l u,~ing the program SHELXTL PC v. 4.2 ! 12 I. 3.2, Mo:tSOCN(i-Pr)2G" 2THF 3.2. !. Crystal data colh,ctimi A red oblique parallelepipcd crystal having the appmxi, mate dimensions of 0.26 x 0.18 x 0,08 mm wan selected and mounted in a 0,5 mm glass capillary and sealed ill a nitrogen atmosphere. Least-squares reliuement of 25 reflections measured at room temperature yielded the cell parameters and showed the crystal to belong to the triclinic sy stem. The lattice and crystallographic parameters are listed in Table I. Data were col[coted over the 0 range of 13X) to 27.57 °. Data were collected by the m scan technique ranging in speed from 1.50"/rain the the weakest peaks to 14.65°/rain Ibr the strnngC S I ~ ~tk:' . r ~ " :~C iulensily standards were measured every 47 reflections drawing no degradation of the crystal over tile data collection lime. Data were corrected for absorpliou using the qt scan tedmique on six relleetions covering the 20range. o¢,2,~, SlrtlcO0'c ,w~hllh~l and v¢l#wntcnt tixaulin,ltiou of the dal:t set idenlilied the o'yslal Its belong° iag IO Ihe Iriclinic space group PI {no~ 2 in Ihe lulernalional Tahles l I 131~ A IhrecMmtcnsioual Pallerson syulhe~is ~as call'icd ~LII and the Imsilions of lh0 luoiybdotuul lltOlllS wPre oblahled ill Ihe a~ynlnlclri¢ unit. The i~osilioas of Ihe rcmaiuo ing nond~yd~geu posilions were revealed hy a Fnuricr dil: l~i'ence utap using Ihe heavy meM atom positions, repealed cycles of full-matrix least-squares reliuemenl were carried out until the relinement converged. All non-Ilydlx~geu atoms were relined with aitisotropic temperature factors and hydrogell atoms wt're lixed at calculated positions.
2,4. S,vmhesL~'fCt'Mo:O dSOCNfi,Pr~:~,
3,3, Mo:O dSOCNlioPrbJ,
A small amount of M%{ SOCNt i-Pr): h was placed iu a ce/stal-growing h-shaped cob and ab{~tlt 50 nd of t~duene were ',~uum distilled onto the red powder, Molecular oxy. ~e=, ,ts allowed to blanket the solulkm t't~r sevee,d minute,,,, resulting in ;in instant color cha,tge l~m~ t~d to a greenishbrown, The hosha~d cell wits outgussed and the toluene was alMwM In evaBwate slowly to the other sideof llte vessel, leaving a dark forest-~.t~n crystalline ptx~luct on the sides of the walls, These cod-stalnwere suitablefor single
3.3. I. ('~:v.vm/dam volh,cthm A dark green rectangular crystal ha~,mg |tie approximate dhzlensious of 0.27×0.15×0.12 nun was selecled aud mounted m a 0.5 mm glass capillary and ~ealed in a nitrogen atmt~nphcrc. Ixast-nquar~s relincment a,l| ~,{ rellections taken i'lxml a i~lalion photograph measured ill mum temperature yielded the cell parameler~ and axM phologl'aphs conlirlned the cell ll~ I~long to tile orlhorhombic system. The hulice and cLwsMIographic paramelers are listed in Table 2. Standard centeriug, indexing and dala colleclion programs were used. Data were collected ~wer tile 0 range of 1.90 to 27.5T' using
A.D. {'~ih'amrra ¢>1~l/. /lllol'k~iillh 'il Chlmh'a A, 'm 2h711e9,S't l O I , l i p
IO3
Table I Crystallographic pamineters ltlr Mo:{ SOCN ( i-Pr i: i l " 2THF
Tahle 2 (71~,ntallo~ntphic parameters for Mo ,( ),i S( X'N I i- I~r I. t
Empirical forniula Color Habit Cryshil size ( Innl i Formula weight Temperature I K ) Cr~slal s),slem Space group Unit cell dilllenxiolls
I-rnpirical fuuriula Culor
C .,tl ~_.Mo:N IO+,S~
red oblique parallelepiped o.2{, × O. I ,'4 x o11,~ ~177.1 29312 t liiclinic
Crystal size I rain I Ftlnrlula v.ei~ht Temper'
I0.3961 2 I I 1.473( 3 I I 1.7791 3 ) 75,liJl 2 i I04.34(2 ) I14 27t21 1221.2151
lk i<'l
/J ("! Vohinle I ~ t I /.
4
I
I nllll
1.329 0.7(15
I"i IXI{I I
512 Sielnen~ R 3 m l V Mo K~l I A -. Ii 71117,1 ..%i lraphil¢ 1.81 ill 22.55
iI
11424 Siemens P3 Mo Ktl I A =(L?11173 A i 7raphile I.q|) to 27.57
I)i ffr:ic'tOilleler u~ed Radialitlli 1%/IOllot'hrltnlahlr tl rali~¢ fill dala ¢olicclitlll I I
~ariable'. 1.5il Io 14.65 in .l Ifill m to
t ineii~iired t'~ er) 4"/relk'¢tJ~ui~ - I f , h:;~fl. 1 2 : ~ I ~ I I , -12~.I~- 12 214h7 22214 I h',,,, -II.11283ci; i al'i,,tlrlilioii 171114 ~IHIII l'lllllil'iuiil [rllin II~ ~t'iili ,~i¢lnrn~ lit ~i¢lii¢lls Pt ~11EI .Xl..l%[i I .~hvldliuk, Iqiilli SIII~.IXI.-I;t I ~hl, hhllk, Iqil,l I ~i~'ilil,'ll,, ~III',I,X'II pl' ~. 42 Iiill.illlilli% It'ilM ~qlililL,~ llll I' %t~tll I'], =: ii']I ~ II,ltllll;141 O i riilillt~ ililltk, I u ~ I ! I o:l I,]/i ~ i II il401~1' I: t, ii.llll11411'l. l~'licre P ~ I I,{,' + 21,; <' i/3 R ~- 1l.l).125. IrR ==ll.914714'.i R ~, 11.1167q.wR -- 11.119141~$ I.IIT~ O,IIIMi. {),llllll O.4:1 I) <1,15
Final R Jltdi~'cs i ribs, data ) R indk'es I all data I (lllUdlles~,o t if. I Jt I.argesl iilld nleiili %I~r Dill a-Ill-pln'illiie I¢ r r:llill Liil'l~¢~t dJller¢lit¢ p¢llk lelA'i I.al'Ge~l diffcix'n¢e hllle le/A~l
1.381 I) 8311
l'({14)1) 1
I'i
• ~can lype Scan slk'ed ( '/lit I l •t~Ciill I'lill~ I"! Slilndl.ird relle¢lillii~ Iliik.x rinll2¢~ Ri'll¢clil,ls lrillle¢led Ilidell¢lidt, lil i'elk.cl iOlis ( )lI.wrved r¢licet ions ('ol'rt, t'l Jiin I 'ell I%'lineiiielll I)illa ledllt'lilln ,~1111tllllt" ~lihllii,ll ~I1ii¢Illl L" Itqill¢ inl.lll Mli t't' ~ 'ilp IK'~ r¢lili¢liK, lil liielllild Qutinlil) iniliilili/¢d Exlin¢liiill ¢lll~ll,¢liilli. I I:l)'dl:Ogl'ii iihllli~ Weilliling st'ht'lne
21.45~( 7 15.630t 3 ) 12.63815 l 423812 I
I)ennity I talc. I I M~/lU ~) AhntlrplJlln cue flJcielll
I)ensity I ¢a1¢, I I M~ ! lit' I Abnoipiillli ¢oellJ¢ Jeni I nnn ~l Dil'liaetolnc.lel tined RadialJt~n Mllnilehronl~ihli ~ tl Range Ior dalli t'illk.¢liOli
dark green rectangular paratlelepilx.'d O.27 x C I 5 xll. 12 8140.89 293( 2 ) orlhorhombic Aha2
Hahit
/>i
/,{AI clAI
('>H ~,,Mo:N+OS~
0.~,34
~ C'illl t) pc .l~l~ln ~peed I / inin I gc'Lill fallt2~, i I •Shnldard ",'lle¢lJllii~ Index ralil2~s Ilelle¢ihlns eulle¢lcd hldependenl ielle~lit ins ( )h~el'ved refk,¢l ioils Absorplhin ¢llrrection Cell relin¢lnelil I)ala i%'dli~'ljtlli ~ll
(o
~ari:lhle: 1.5 tt~ 14.65 m ~,~ 0.70 in o~ 3 nleasurede~r) 47 reflections
25h7 qR,., ~: I).[)tlr~' ) 1~1)2 S¢lttJoellllpJrJ¢;ll frtiln I/" ~l.illl,~ ~lelllell~ p?i Si¢lncn~ XI)ISK glllil+Xs xh I ~hehhiek, lilq!ll ,%III{I.XI :lJl I Mwhlliek. Iqq ili ~i¢lllCllS SIiI'.I+XTI I'(' +. 4,2 lilll nllilli% I¢il~l ~iliiiilt.~ I,II I II [)(Ill(till ? ) I+idlli7 ililld¢l u ,-+ I/i,r'l
I,,'i
+ !llll,lll4Pi
+ *ll,lIO(IO#'l,
~,i,ht'lV I 1~ I I ,,' + ~/+L I f I RI ": il,il44,1, ./72 : II ii'/bll4 R I " II,IIVLI2, nR2 °" li litl 17 I .llJfl
Final R ilidiee~ I I :' 2it I I I I l? illtliee~ I ~lll dlila ) (hllittlles~.t~l.lil till I .tll'lJ¢~l and nk, illl .~ I ~r D;il;i-h l-p;.ll;in lelL'r l'illJo I ar~¢sl dillerenu'e peak (e/A') I .iil~¢sl diff¢lent'e htll¢ [etA'l
- 418t14.111124
O,1:1 lLhB3 o 3xJ
3.3.2. Slrm'lure sohtlima and re#nement l:,xmnination of the data ~cl idcnlilied lhe cry~i~l as belonging to Ih¢ t~rihtu'httmhic x p a c e g r o u p A h . 2 I no. 41 in II1¢
Ihe ~o s c a n t e e h l l i q i l e
w i t h il V a l ' y h i g scan i'iit¢ i'iiliTJng I r o l l l
1 . 5 0 ° t I n i n f o r ilie w e a k ~ s t p ¢ i i k s Io 1 4 , 6 5 ° / i i i h l esl p¢liks, T h r e e i l l l ¢ l l s i l y r¢lle¢lions showing
[ o r the SllOllgo
,~liilldards W~l'¢ i n e a s t l r e d eVel'~ 43
no discernible
d¢gradaliOll
o v e r Ih¢ c o l
leeiJon l i m e , I ) a l a Wel'e ¢ o r r c ¢ l e d for a b s o r p l J O l l u s i n g i/r sol.ill illfornliilJon oil six
rell¢clions
¢overhlg
the 2 0 rilllg~.
inlermltionul
Tables)
1131. A t h r e e - d i m e n s i o n a l
Paiter,,,on
s y n t h e s i s w a s L':lri'il2d Out a n d the p o s i t i o n s o f the niolyl~deo 11LIill iltOills W¢l'e o b t a i n e d
in the a s y m m e t r i c
Ullit. B y IIS,Jll~
the h e a v y met:tl a l t ' m p o s i t i o l l S a F o u r i e r d i f f e r e n c e calculated, hydrogen
rgvealing
the p o s i t i o n s
limp was
o f the r e m a i n i n ~
non-
alOlllS, R e p e a l e d c y c l e s o f f L l l l - m a t r i x l e a s t - s q u a r e s
1(1,4
A.D. ('lh,alerra i,t ill. I him'l/l,ni 'a f'himlca Achi 2:671 lOq,~) 101-107
relinement o n F ~ were carried out until the reliiiemeni converged. All non-hydrogen atoms were relined with ani.,~)impic temperalure factors and hydrogen atoms were lixed at calculated positions,
l
4. Results and discussion 4. I. Synthesis und characterization
F
Fig. 2. Stereo packing diagr, un of Mo:( SOCN( i-Pr )~, 1 : 2 T H F .
The reaction between stoiehiometrie amounts of Mo:(O:CCH~)4 and the monothiocarbamate salt. LiSfK'N{ i:Pr);, in ethanol results in a red product lbrmulated to have the elemental coml~isition Mo,I SOCN( i-Pr): I.~ ba~d on elemental analysis and the single-crystal study. The preparation of this Mo( !! ) complex is similar to the methods of Steels et al. 131 and Ricard st al. i 41 for the prepanition of .~veral dinuclear niolybdenum compounds having the general torinula M=,L4, L = S:COEt. SOCPh. S,CNEb). A small quantity of Mo4 SOCN(i-Pr):)4 dissolved in toluene with trace amounts of oxygen afforded a dark green crystalline compound having the composition Mo,O,o I SOCN(i:Pri ~L. The preparation of Ihi~ Mol V ) complex i~ .~imil:ir to the metht~l of Cotton et al. 1141 and Baird and Croll 1151 for the preparation of Mo~OdC~H, NSi4 and Mo~O~( S~CNEt,)~, respectively. A thermal ellipsoid plot of the molecular structure of Mo=,ISOCN(i:Pr)~I~.2THF i~ d&phlyed in Fig. I and a ,~lereo packing diatlram i~ ~hown in Fig, 2, Fhlal illOllliC cooro dhlaie~ lind lelllpcrldure facl,~r,~ are Ii~led in Table 3, Selected bond lenglh~ and Imgle~ I,,¢ listed in Table~ 4 and 5, i%;~!~¢= l i v e l y , l = ~ i i m i i l e d l l i i l l d l i'd d e v i l i l h l n ~ d¢l'i~¢¢d f f o n l Ih¢ It, f i l l . ~qtltl~
,intlly~i~ a p D e a i ~ tn llarciithe~e~
T h e u n i l c e l l i l l IVl~h01 ~ O ( ! N t
' t i l e r c'ach Illtlntlt~r~
ioprl: I,, ~TFIF
¢Onlliin~ oi11
Table 3 Alomic ¢~mrdinal¢~, i x I11~1 and cqtlival¢lll i~oll'~pi¢ dir, placcnlenl c0~efli. ¢ient~, i Jr' × I(t~l lot lkhbt SOCNt i-Prl: I ? 2 T H F Atom
I
Mo S( I 1 ()l I ) ('l II i
I
."
552~! I 1 5116£,~3 t 37591 £~1 4187101
5~145t I t 51(Gt 2 t 291314 t 3-11i516 I
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26061 5 I
('l ('I ('i ('t CI
44331 .14531 Iq12t Jlllll 43521
,',1641SI 1274171 f~13114) 2f~t)ll l(ll 322011~ I
121 13i 14t 15i If~t
121 131 121 IJi I3t
I sq
521151 I I f~441114 I 737016 ) 844815 I 8112181 85..11118 I
79881 ~ I 111221h S i
81117 i
71161 ilfll
7
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111321118 I 5(~1il I 2 5,~8J( .1 I,I }f~l ? fl7qfll tl
51~3t 5oi 5 i 5,
5~14111 I 21
ill511 o I
Nt 2 t Oi 2 t ('( 21 I Nt 2 i
f'ffv,lli~ ,t I 7f~ 1416t 71,11~I 1 I I I Ill 2~11q I
.15~111 ~ t 5~9491 4 I 4~1~1 7 I 4~1121 ~ I
( '1 ~ I
~tjllnl I I !
III1~ I I ~ i
('l 211 {'i ~4 t I'l ~1
'14741 1.11 Illtllnl I11
JTJ~l I,I I lll~lllqi
71 i l l X (iNfll II i)
(it,l(~i ~ i id14111 ~ i
~}11f,I ?
I 'l ~f,t
~14171 II t Ilil I~1 lit,
11 }=/i Ihtl'l
IIIN4Ol I I i (~i}lllll
71bl!li ,~ t ~ll?(lli
~.h I i
(141 fl I
171 ~ 1 ~lll fll 1i~t % I '141 1 t
CIl~Si f¢1481 lli i 811~51 }11 7~tl! 131
•12~ I i 5411 ) 5ol 3 i 4t~f 5 I 5,'41-11
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('1 171
{h ~Ti ('1JTt 1't Xl't
a
~1'1.12! I } I 1111871 151 ~1211bl~121
f~ I1~1 IIII fi??,ll I 2
I .~qi iI 1 ItIM ,q I
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5 t d l t 141
t°17i =#i
' I qtlivalcllt ik~m'npiL , iI ' d~'lallt'd il~,i~ile Ihiid ol tilt" tl~,ct' ill Ihc ~llhl!),Ollilli#~,d I I It'll~lil
Cllli
Tilbl~" -1 I1~ id 11 I~ll ~ I ,\ i liu .llt~l,i Ni I! 'N t i Pi I, t i ' 2<1'1II
T'qu. M u ~ A i I%b~SI2AI
Fig I. lllt~tmal cllip~nid t~Inl ~t lit, qitltltti,c ~1 M~bl S(E'NI i . l l r l . t • 2 T W . Tli¢illlal cllip~fd~ a~v ~ht~u~ al lilt' ~It*:7 Dl~ll~bilii) lc~cl, It)dm.~2t'li ttl~lll~, tl.tl~,.~l ~ h lilllilltkl I{q' elatily.
2llO?~l:,j 2.171~12~
Mo{)¢IA! ~ I b t'l I I !
2,1j2|41 I 74~1Ii~
I'~ II ! NI I ~
1,15?tt4~
N~ I i {'t I 1~
Nlll ('lli~l ( ' q l t ~ ','ll.l! ('l tf~-('~ 17~ ,%121 M , 4 u A I
I~{iX! ISlSII2~ 1,5tt7q I t I 2,471~12t
1't12t ( ' t l 3 t 1 " t ~ 1 l'llt~t S~2t-,('i 21 ! I:~121-('121~
1:|8111~1 1,51S~121 152':,112~ 1.7a,l171 1.2711181
Ni 2 t o-('~ 21~~ Uq21~t.-I'I2Tl i[tt I1 b4.'l 4T~ ('1 21"1-4.'t 3"!~ I
1.48518 t 1.5111t I I ! 1.3ldl 131 I 41~2t
('~ Ill CI ('~
15131 I I ) 1.3741 II I 1+.18111131 1 3~L21
22 t -('t 23 ! I r t . ( ' l IT I ITI ('12|*1 .11 ~-(', 41"1
A,I), Cah'merra el al, t lmu:¢mm'a ('himic. rh'ta 267 ~1918) lot. 107
105
Table 5 Bond angles 1'~) Ior Mo:( SOCN( i-Pr), )a "2THF S( I )-Mo-O( 2 ) OI 2 )-M(r-Mol A ) Ot 2 J-Mt~-O~ IA l
86.57t 14 ) I(X).ITI 12~
S( I I-Mo-SI 2A Mo( A i-Mo-SI 2A
96.n3t S ) 92.37~ 6 ) 103.7121 120,315 } 119.2161
St I I-Mo-Mo~ A I S( I ~-Mt~-OI IAI Mn( A )-Mt~O( IA ) OI 2 I-Mo-S( 2A ) O( I A )-Mo-S( 2A ) C( I I ) - O I I )-Mo(A) S( I ) - e l I I )-N( I ) C( II I-N( I l - e l 13~
88.51 21
Mo-S( I )-el I I S( I I-C~ I I i-O( I ) OII I-C| I I i-NI I ('t I I )-N( I ~-C(16) N{ I )-17~ 13 i-(.'~ 12i C1121-C( 131-C1141 N( I I-C1161-C1171 C121 )-$12 )-Mo( A ) S12)-Ct 21 )-O(2) O121~('121 t-NI 2~
121,616)
C( 13 l-N( I )-C116) N( I )-C( 131-C1141 N( I ~-C( 16)--C(15)
112.9181 113,3(8) I I 1.7(8) 11)3.41 3 ) 120.7171 18.71 f~)
('I 21 )=N( 2 l=,k'l 21~I
21,{~16)
Cq 22 )-('( 23 ~-('{ 24 NI 2 I-('126 l-C( 27 l CI IT)-O( IT~-('(4TI
I 1,818) 12.5181 12.6q 6 ) 10.418 )
C( 15 I-C( 1 6 ) - C ( 1 7 ) M(~()( 2 l-C( 21 I S( 21-C121 )-N[ 21 ('121 J-N( 21-C1231 ('q 231-N121-C1201 N(2 I-C123t-C124j N(21-C(26)-C(25 I ('q 25 ~-C( 26 I-C'[ 27 I ( h IT)~Ct IT) C[ 2T)
n14.lh I I i
('I 2'I')-('(3T)-C'(4T)
Cq I T l-C( 2T )-Cq 3T O( IT l-C( 4T t4"( 3T
III.6(7~ 113.8(71
106.6(I0) 110.2113~
In7 7~ 12
Table ~'~ M*~-IVloboml di~,l:uwe~,h," M J. ~" 21/
Coml~mml
Moq.' I A )
Mo-Mo l A I
RcI.
Mo:t O,('('F, ) a" 2P) Mud S,('OI'I I~" 2TIIF M~d ().('Ph) ,. 21 digl~me i Mo4 S:CPh ! ,. 2'I"I II; l~h~! S~CMe I ~. 2TIIF
2.54,~ 18 ) L705[ I ) 2 6631t~) 2,72717 ) :?712t (~)
2.120! 2 ) 2.1251 I ) 2.11101 I) 2,1301 2 J 2, I~ h I ~
116 I 14 l 1171 17 l I 71
~'enll'nsynmlvlri¢
92,21¢61 167,151 II 1110.33t ] I ) 16"/.119112 ) 86.3~ 2 ) 122.3~4~ 120.5t5) 12{1.1~6~ 118.116~ 112.0~8) 111.3t7) 113.7(8) 121.8(5) 120.6( 6 ) 121,2171 I It~.917) 112.3~8~
i n o l e c u h ; , "|1he M o , ( S O ( ' N ); ~'ore o1' the
n | o l e c u l ¢ pnssrn~es nearly ideal I)fla ~,ylmtlelry. T h e Mrtictare o f the I n n l y b d e n u i n lilnl~olhiocarbziln~.|t¢ ¢ o n ) p l e x i ~, s i m i l : l r
Increasing the strenglh of tl~e metal-axial ligand bond must restlll in the melal-m:.tal bond lenglh. This lel)glhening of Ihe nlelal-lnelal bond is nmximized when Ihe axial Iigand in Very ele(.:lrOll withdrawing and the other ligands are very go(xl electron donors, as in the Moz(O,CCF,}4.2P ), complex reported by Collon and Norman 1161. The sleric and elec° Ironic properties of tile ligands themselves might also lend to Ihe lengthening of the Mo-Mo bonding disu:..,,x A Ihermal ellipsoid plot and a stereo packing diagram of the t|ltflecular sli'tt¢tul'e of MoXid SOCN(ioPr),), are displayed in Fi[~s, 3 and 4. respectively, I;inal atonfic coordinate~ CI6J
to Ihe ¢arboxyhzte ~ol|lpLl|llld~. h a v i l | g Ihc ge||eral f o r l n u l a
M~L,,,21J. The Mo=Mo dislance of 2.112(1) ,~ for Mo~( SOCN(i°Pt') ~L;' 2TIIF i~ ¢OllSiSletll with those lisled in Table O. The subslilulion of the softer base sulfur for oxygen in Ihe houdin~,, ligands shows no signilicam change on the Mo-Mo bond dislance. The Mo-S dislances of 2.481(2) :rod 2.474( 3 ) A in the Mo,( SOCN(i-Pr) ~L;" 2THF comple× do nol signilicantly differ from those of the dilhiocarboxylate compounds or the xa,lthates, which have average Mo-S dis= lances of 2.465( 81 and 2.477( 2 ) ,~. respectively. The MoO distances of 2. 119( 6 ) and 2.130( 5 ) ,~ are also reasonable values to the average Mtv--O distances found in Mo2(Ofl?CF,).;'2Py 1161 (2.116 A) and Mo:(O2CPh).,' 2(digly,ne) 1171 ( 2.107 ,~). The Mo-O(THF) di.,,lancc of 2.690(6) ,'~ could indicate a weak inleraclion belween Ihe molybdenum and tetrahydrofuran. Tlus is generally the case when axial ligands are bound IO a molecule posmssing a very strong M-M quadruple bond. Collon el al. I ]81 have reporled that the auaehmenl of axial ligands Io co,npounds having Ihe general fornmla M2L~ slightly lengthens the M-M bond.
:c31
Fi B. 3 Themlal ellipsoid phil of Ihe slrllcltlr¢ of Mo,()d .~O(*N(i-pr), I,. 'rhernml ellipsoids are shown at the 50r/~ pnd~ability level. Hydrogen arums have becrl olnillcd lor ¢larily.
A,D, ('~dcatPrr++ e! al. / Im,'.+anica Chimica Acla 267 (lO0,e,) I O f 107
I(J~
< N Fig+ 4. Stereo packing diagram ~)t' Mo,O ( SfK"N( l+Prl: I+~ Table ? Atomic cm)rdinate~, ( x I0 +) and equivalent isotropic displacement coefli~'ient,, ( A × I0 ~) for Mo:O+( SO~N( i-R'): )+ Atom
.i
y
"
U,,, "
O( I )
~(XX)
(1
31 ( 2 )
Mo O(21 S O N C(I) (?121 C(A) f(4) C(A) ('10) ('(?) S'
416.1(I) ~889( 2 ) 4309(I) 44.~7( .I ) 4659(3) 44~5(41 4702(5) 4407(~) M$111~)) 47741¢)) ~]4H(~) 41q5(5) 11'169(11
273(I) 361(3) 185|(I) 734( 4 ) 206615) 15211b) 2081)16) ]567()~) 311qt(8) 17,%(~)) 117~(X! I ]q~(~)) + 1144(1)
196(5) = 105217) 370(5) 182g( 7 ) 2426(8) If~l(8) 2183(I0) 2947(12) 2178< 12) ~5201 O) A,~)/~t)(I111 ,I0~0< 111) ~),'-)(~)
34(1) 47( I ) 48(I) 48( I ) 55(2) 45(21 o4(3) t)](4) nTt4) 6014) 8411) I114< 4) ~111
N'
271~4( ,I )
- ?t),~( 5 )
I )~761 (4)
(~412
(~tS) ('l ] ' ) C14'1
273~1 ~) =~?t~(?) ~11)~1~1
t7(13(?) = I~,~4( I11~ - ~=14,~1In)
~142( II1 ]~2112) I,~il( 131
F)1(3 111i,115 11"115
CI0') ('(?')
1'4.1~15 ) 2562(0)
198181 454(.~)
13931131 ](M~)t 11 )
11181,~ 111114
(1
Table 8 Bond length,. ( A ) for Mo,O ;( S(K:NI i-I)r ) : ); Mo-O( 2 ) M()-,,O' M(~S' O=C{ I ) N 4 : ( 21 N-C( 5 ) C( 2 )~('< ,~ ) C( 5 )-('t 6 ) O';C(I') N'=('< 2'1 ('( 2' ) ( ' ( 4' 1 C( 5' )+C( t)' )
1.68915 ) 2.131 ( 51 2.441 ( 2 t 1,252( IO1 1.492{ I I ) 1.4%1131 1.52f)( I ,~ ) 1,531 2 ) 1.27<)( I01 1,457t 13 ) 1,54( 2 ) 1,481 2 )
and temperature facto~ are list~ in Table 7, Selected boml lengths and angles are listed in Tables 8 and q, Estimated standard deviations derived ia)m the least+,,~luaresnnalysis appear in parenthe~s alter each number, Four m)n-centrosynllll~tric molecules occupy the unil cell of Mo.,Od SOCN i i-Pr )., ).+.The general structtm~'of the mol~.'~uleconsists of two dimarted octahedmi sharing a hridgin.~ oxygen ~ ) atom, which g ~ s to I\mu an almo,~tlinear Mo-O~M~) bond having the angle of 1~4.?t4)" A second, terminally bound oxygen (0,) atom along with the two sulfur attmls aM two oxygen atoms th)m the m~mothiocai~tmate ligands c~+nplete tbe octabedral enviromBent about each of the molybdenum atoms, The tenainally bound oxygen atoms
1.8621 ( I I ) 2263( 6 ) 2.4%( 2 ) 1.752(81 1.342( I(11 1,51 ( 2 ) 1.51112 ) 1,74~( q I 1,325( I111 I ,.184112 ) 1,5512 ) 1550,t 14 )
'taM,: o l|olld iu1~lP., I ' i (.111Mu +1),t N(B "Nti lh 1. I + Ill -~1 M~+.(ti I ! (hll, Mo It' Ill I )=Mo <')
III/i. Jl ,|
ih2)
( l t ~ l M o S' O' +Mtt,-S* O! 2 l+Mt)+S O'=M~)-S S'+M~+=S
Itl'.~.ll
( h I F=Mt) S' 0.- M;)+S' O( I o.,M,a,: ~ ()~M~+S 'Moo* (h I ~- M o r a l ('~ 1 t+O+Mo
++)4,'+,)2~8) ;},~.|)( ~ b tjtt,,?3! 5 I 04?(2) I(d,?(4 ~ I(Hk3( 5 t
('i I r N -,('t~ !
12oxt ~)I
O.~('t I ) o N N , ( ' t I J+S N C t 2 )) +('t ,'t I N+('t 51+('~ ? I ('~?} -('i 5~-C161 ('t I' leO'--Mo ('~ I +))-+N' +('t ,~+ ~ O'+CI l'b+N + N ' - ( , t I' b-.s" N ' - ( ' ( 2" ~-o('t V i ('tot' ~ U ~ 5 ' ) - N ' N'+C( 5' b-C( 7" I
12 I,('~t S i
~)L612 t~4,2~2 I ~4,11?t,
(St I )-S=Mo
12(1,5q 8 ,' "l]quWal+llt im,,tr,t)pl¢Ud¢litlmJ a~oBe lhirdol'lhe tru)¢e of|Ix, v~ilhog).t,nalized (~/,)I+lff~,l~l',
~ho=O( I ) Mo-O M(~S S+C( I I N-C( I 1 (7( 2 ) =(7141 C( 5 )+C( 7 ) S'+C( I' ) N'o+C( I'1 N '-CI 5' ) ('( 2' i - ( h ?,' ) ('i ~' i ( ' l ?' )
('( 2 1 N-.('~ ~ ) O-(:'~ I 1.5 N-(,~21 ('14 I~ 1,9181 N - ( ' ( S r ('(+~)
(?t I' )+,S'~Mo ('< I' ). N'-('t 2+
I Ins( ~Ai ??,91 ,~I
('~2').,N' ('(~'l (~'-(,t I + t-S+
N'+(,t 2+ F ( , t a , ~ ('t 4' ~ ,('12' ~ l.'i ]' )
I124~II! 11t),(~( I I I 112,{~1 II11
'M,), t Y
~)? ~(2)
122,q17)
I I I,(+t q ) 112,1tq) 114,q( 12} I(11.+~45 I 1211,?(8 i 122,2(8b
124.3( I12,~( II,LTt 1 I0,7i
71 II~ I0) 8)
have an average M~O, distance of 1.689(5) A, and i)ave considerable multiple bond character a.~discussed by Cotton and Wing 1191. The temfinal oxygens are cis to one another acn+ss the Mo-O-Mo bridge and are directed slighlly away
A . D . C . h ' a l e r m el (~L / h.)r~a)m'(i ('himh u A t t a 26 7 t I ~IVSl I Ol -. 107
Iil7
Table 10 Average l~)nd lengths and angles oI related ctmlpnunds to Mo.,O d SOCNI i-Pr ~: 1,
Mo-O-Mo i ') O,-Mo-O~, t") Mtv-Ob ( A ) Me-S,, ~A ) Mo-S,~ ( ,~ ) O, geomel D'
Me--O-Me ( ~') ()~-Mo.-Ot, ( ° ) Mo-Ob (At Mt)-S,, I t~ ) Me=S,, ( A ) O~ g¢~,),lletry
Mo:O,t S:COE! ), 1221
M,:O,I S:Pt OEt ):l~ 12III
MOO,, S:CN(Pr), h 121 I
17K03 ±4.n6 103.74 ± 2.117 1.862 ± O.(MS 2.702 4- O.01 2.486 + 0.026
linear" 1113.11110, 1.863( 12 ) 2.801 t 5 ) 2.495 ( 9 )
178. I ( 7 ) 102.918) 1.863118 ) 2.6781 5 ) 2.465 ( 14 )
,'is
tra,x
cis
Mo:(),! C.H,NS )~ 1141
Mt).Od 2-SC~H,N-3-SiMe, h 1231
linca~ ~' 105.912 ) 1.853q II 2.3115151 " 2.18515 ) ' I'),(tlz~
linear ~ I05.O( 2 ) 1.8631 I ) 2. Iq9151 2,491112 ) and 2.452t 2 ) ' ( i.~-
Exact value not rept~rted. ~' Mo-N. ( A ). • Me-N,, i A 1, S,, = sulfur Irtm~ It) ()~. S,, nalfar ci,s It) 0,, N,, =' nilrogca Im#,.~ to O,. N,, :: ,,ilroge,i (it h) 0,.
from one another. A t r a . s relationship of terminal oxygen atoms can he fonnd in Mo:OdS:P(OEt)2).t 1201 aad blozOdCsH.,NS)., l l4l, indicating that both the ('is and t m n s arrangements are generally possible. The average O,Mt~Ot, angle 197.512)°) is in good agreement with previously reported valnes. This angle is it result of repulsion between the lone pairs of electrons on the Mo~O bond and the lone pairs on the Mo=O hridging oxygen atom. The n1ononleric nlolybdenum conil)lCx of Mot)z( S:CN (Pr) o:).: 121 I also exhil~ils {111 O-,.Mo. 0 ilolld an~l¢ o f 1()5,7( I )'~, w i t h i n re|lsonllbh.' p l ' o x i n l i l y o f IIl~ 9"],~ ') reporh.'d for llle d i m c r i c lllltlitl~,
II i,~~,if ilitOl't-'xl IO nlllC
t h e t¢l')llhlal o x y g e n ) t h a n the ('Li M o O
thai
lilt.' Moo-Ob l i n d s
II'tltl>; IO
a l o n l are s i g i l i l i c a n l l y Ioll~¢r ( 2,263( 61 di,,,lam:¢ t)f 2, 131
( 5 ) A, T h e iiierca.,¢
oI' tile Me-4) bond/ram' h) the Me4), bonds i.~ a genCl'al phenomenon l'ound lhmoghoul the Mo~Odl.l.).) colno l~)unds. Rehlted bond lengths and angles IO the Me:O,. (SOCN(i-Pr).,)~ compound can be found in Table I0. Tl~e single-crystal struclure oI' Mo2Od SOCN(iopr), ).~ is nnique in the fact thai no other compound in Ibis class has chelating ligands attached through an oxygen atom.
these types o1' compounds have been delennined and arc reported here. References I I I t-.I. Sliclcl. I)rog. Inorg. Chem.. I It.~77 ) 22. 121 T.A. Stcpheuson. I-. Ilatmistcr and G. Wilkinson. J. Clwm. S,,.',. ( 19641 253K I~1 D F..%h.'¢h: lll|tl TI~, ,%tepheI,~ol,. lao, g N u l l ('h¢l|,, I.¢tt,, 9 ( 197=~1 777. 141 I. Rieatd, P, Kara~'ian.idis ,rod R 9v't.ls., htorb! ('hen,. I j ( IqT~,l jlTq, 151 I,. RMud, J. I;stiL',l,le lind I'L Wt'tn.~. J ('heul. Stw. ('h¢ln ( ' 'mmn, 11972 ) ')!X),
Iol I R itmrd, L 1~!4i¢,l,K!'imd R, Weiss, h,or¢ ('he)., 12 t I t.~73) 2 1 ~ 171 F,A Coll.,,, P,II, I=aav~i~k. RII, Ni~.a,,d¢l Jlid J (I, Sekah)v,~,ki~ ~ehl Chem. Seaml,, Set, A. 32 1 19781 66~
I s l F, V¢lht mid J, Zt, biela, J, ll,nl~. N.~'I. ('hem, 4l) t Itrls ) 4~7 191 (;.Z, Ilol~K,. Z, Aa.r~. AIl~, Cheat,, 5? ( 19761 42K I01 S,I.. Hawthor)|¢, A.H Brudzr and R,C. Fay. h,.rt~. Chem, 17 ! p)TN) 2114. I I I A,B. Bri~n.le aud F.A, ('olll)n. luorS. Sylllh., 13 11972 ) 87, 121 L. Mess~rl~. Chem. Rev,. ~18 (Iq~X) 1"129. 131 D, Cou~ouva, is. I)rttg, hmrg, Ch¢ni,. ")6 I I L)70 ) 30 i. 141 I : . A . C . t t o n , P,I-, I:allwil.'k illld J,W, Fitch. It'.)rg, ('he,l|,, 17 I I gTHI 3254.
5. Conclusions Replacemcnl of the ace(ale groups by the )m)nothiocarbamate ligand was shown to form ;icompound having the general formula Moz(SOCN(i-Pr):=h. The dinwric species maintain the original acetale structure ahmg with the shor! Me=Me bond length, indicating the strong quadruple hond= ing between molyhdenum alon|s. This dimeric compound was also shown It) undergo a reaction with molecul',u" oxygen to form Mo~()d SOCN( i-Pr)2 )a. Crystal structures of both
1151 I)M, Baird and S,D, (?roll. Polyhedr.lL S (19)46) 1931, 1161 F.A. Cotton and J.(;. Nol"nlaI,. J, All1. ('l'ten,. So¢. 'M ( lt172 ) 51~.J7. I 171 I).M. Collins. F.A. (,otlo,I alid C, A, Murlll., I,lor~. Ch¢,ll.. 15 t 1976 ) 2¢150. I INI F.A. ('tilt(m. M.W. Iixtille and I..I}. (;age. I,It),~d. Chem.. 17 (197M) 172. 19I F.A.C.tt,n aqd R.M. Wing. In,r!:. Chem. 4 i ItU)S ) x67. 2nl J.R. Knox a,ld C K, Protlt. Acla Crystalh)gr.. Sect. B. 25 ( Iq69 ) 2281. 211 I., Ricard. J. l'Mienne aud R, Web, s. J. Cootd. Chem., 3 ( 1974 ) 217. 221 A.II. Blake, F.A. Cotton a,,d J.S. Wood. J. A,11. Che,n. See., 86 ( lqbJ, ) 3O24. 23l F. Bh)ck. M. (;¢r,a,). II, Kang. G. Oh)ri-Okai aim J. Kuhich). Im),~ Cllenl.. 30 ( 19111) 17311-1747.
InlwganJea ('him)ca Acia 2{~7 I Iqt)HI 11)1-11)7
Synthesis and characterization of molybdenum(II) and molybdenum(V) monothiocarbamate complexes. Crystal and molecular structures of tetrakis (isopropylmonothiocarbamato) dimolybdenum ( II ) and oxobis [ di( oxoisopropylmonothiocarbamato )molybdenum(V) ] Anthony D. Calcaterra, Scott B. Kimble, T.L. Groy *, T.M. Brown * Ih'parltll¢lll o/{'h¢itil.~tl:v t/lid II.ichemi.Wrx, /hll ,~71 filM, Arizona .~t.ll' UmrerJitv, Tempe. AZ ,~52,~7.1604. 1/571
Reg.'tired 2~ N~l~,:eillher ItY~fi: accepted J March I*)t)7
Alistrllet The compound Mo.( SOCNR: )= ( R = i-Pr ) has heen prepared from the reaetitm of a ,m)ichit)n)ctlt=." ~llllOt,lllt of lithium monothit~arbamate will) M o : l O,('CI~I ~).= in ¢ihluiol, The con)pound was then reacled willl molecular o,xygcil Io fornl the (~xidized product M o : O , ( S O C N R : ).=.
The strtiettll'e of the isopropyl derivative l~tir'i|.~i+btained US)hi sinllc-¢ry.~ial X-ray analy.~i.~. Moq SOCN< ioPr): )+. 2THF crystallizes in the Irit'lini¢ .~llat'e gl'~mp PJ wilh Z + I :uid unit call diln~llsions +l = 1l).3tJ61"il A. h= 11.473(3) A. (.= 11.7791 3) A. (i + 751)312)'. = 1(M.34( 2 i <~,? = 114.2712 )" and V = 12'~I.=l( 51 A '. Crysiallogi'al+hic sitidie~ lia+e also b~cn conipleled fiw the MoX).I S()CN( i-Pr i: I, ¢Olltplex. which t'l')sttillitcs ill Ilic orlhoihiiinliit: sp:l~e +i'
I, |ntrodl|etiou The most recugnized t)l the letrllkis(carl'~oxyhllo)dirnt)lyhdcnum(ll) compounds will) Mo=M,~ quadruple honds is letraki.~(acelato)diniolyhdenul)l 11.21. Mo:=
(O~CCFI~)<~. The diamagnetism of the carboxylates alotlg with a significantly shod Mo-Mo distance indicate~ a direct metal=metal interaction. In order |o satiM'y the 18 electron rule, a quadruple bond is fornl)dated to exist between the metal atoms. The ease of replacement of the carboxyl,'de groups, the high unsaturability due to the qtmdruple bond and tile low oxidlllion stale of tile metal all cotitrJbute to the fact that these species have become excellent precursors for further reactions. ]'he number of compounds containing lhe M o ; = ' n)oiety, with a quadruple bond. isquite lengthy, showing a diverse range of coordiu;ttiOll with both monodenlate mid bridging bidenlale ligands. The replacement of tile acetales with uuivalenl bideiitate ligands, such a,, xanlhales ( S z C O R ) . dithiocarl)amates (SzCNR..,), dilhiocarboxylares ( S , C R ) and nionothiocarboxyhites ( S O C R ) , were ~ CorreMxmding auuhtw~,.Tel.: + I 6[)? t~l"~53461: fax: + I 602 (~()5Fl6()7. (X)20-1693/98/$10.n0 (¢~ It)08 F.l,,,.eVJ¢l,Science S.A. All rigllt~, rosen'veal PIISO020- 1 0 9 3 ( q 7 )05561 -8
initially investigated in the early 1~7() ,, 13'~l. TIw major eil|lllta~i,., was to Jilve,',,lJ~lt¢' w h l l l cf'iccl tilL' rel')lilCL'lilelll ol i~("(), by R(]S, or R(TS(:) nlighl have Oll the I))¢'tal-loo metal holtdillg, and if, in filet, these i1¢w ¢OlllpOllnd~ wonld retain ihe JlIIIJLII "il¢~lill~,,lyrl~' strlll21Lir~ or possibly uudcrgo an oxidativeoaddilion reaction, as discovered by Wei~,s and co-worl~ers J61 it) 1()72. A less frequently ¢ll¢Ounlered ligand, monmhio¢:lrbamate ( S O C N R , ) , is a univalcnl hidentate ligand oh'selF related Io the wellocharaeterized dithioearb:mlale ligand. Monothioqarbamate ¢omplexe,, h:l,~c been prepared only since the early IqT0s, with ;lltentilm ten lered primarily on the litter transition mctab,, it was therel'or¢ o1' interest to investigate the reaction of M o : ( ( ) ~ C C H , ) ~with the litllium isol:~ropyhlionothiocarbamale .salt to determine if Ihe proposed compound. Mo.:,( SOCN( i-Pr ): I~. would main° lain the original acel;.lle slructure or p¢)ssibly undergo the oxidative-addition reaction similar to the dithiaearbamate work of Weiss and co-workers 16 I. The isopropylmonolhiocarbarnale derivative when reacted with molecular oxygen forms a con)pound having the ;ormula M o : O , ( S O C N ( i Pr):).~. The structural properties of this compound were ab, o urMer invesligation.
102
AD. Cah'aterr, et ld. / Inor~amcaChimwaActa267 f l!~8J 101-107
2. Experimental 2.1. Preparatitm t!l'mot~t,thiocarbanmte ligand lithiun~ N.N.dii.~opropyhnonothiocarbamate. Li( SOCN( i-Pr),_) This particular ligand cannot be purchased commercially, unlike the ditl:l~ca~amate analog. The monothiocarbamate ligand was prepared according to the method of Hawthorne et al. [ 101. 2.2. Preparathm ¢~'molylnlemt,1 acetate dimer: tetrakisl carl~m'htto Jdimolyhdemun( ll ). Mo :( O :C CH d ~ M,olybdeaum{ I!) acetate was prepared by the literature ntethM of Brignole and Cotton ! ! I !.
2.3. Synthesis of Mo:tSOCNfi.Pr):)4 Mo:( O=,CCHj ) ~ ( 0.65 g. 1.5 mmol) and LiSOCNI i-Pr), t l.01 g, 6.! mmol) were loaded into an extraction vessel. The vessel was outgassed and approximately 50 ml ofethanol were vacuum distilled onto the reactants. Stirring the solution tbr alx)ut 12 h pr~xiuced a dark red solution, The mixture ,~parated into a dark greenishobrown solulion with an insol. able red powder .~ttling to the bottom. The solution was decanted to the other ~ide of the vessel. The solveltt was distilled back onto the original red powder leaving a dark greenish-brown residue behind, This process wa,,, cominucd tmtil the sohlltnll tlbOVe the solid pl~tict was relatively colorles.~', three or four eXtl'actioli~ Wel'¢ '~tifttciellt, Ethanol should not he leli on the product tier long periods a~ uiid~.,sh-. able l~Olll~OUtld% l a y I'orm or cause dccollll~i,dlion of Ih¢ desild i,toitl~nd, The ~ihlinol was removed and tile vessel was l i m l ~ d in v,,ioJo for approximately 12 h. The vessel was brought into the glove I~lx and the Mo:( S ~ N i i-Pri: i, wits stored in a ,,~rew cap vial, Yield 0.82 g. 65¢~,, Anal. Cute.: C, 44.26; H, %38; N, 5.74', S, 13, i I. Found: C, 44.25; it, 7.58: N, 5,74: S, 13,54~'~-.
3. Structure determination 3.1. Single-co'sml X-ray studies 3. I.I. General The diffractometer setup used for all single-crystal X-ray studies was a Siemens P3. The diffractometer was interfaced with a microvax 2000 computer, containing all the required software to collect and process the data and to solve the structure. The structure was solvc~l u,~ing the program SHELXTL PC v. 4.2 ! 12 I. 3.2, Mo:tSOCN(i-Pr)2G" 2THF 3.2. !. Crystal data colh,ctimi A red oblique parallelepipcd crystal having the appmxi, mate dimensions of 0.26 x 0.18 x 0,08 mm wan selected and mounted in a 0,5 mm glass capillary and sealed ill a nitrogen atmosphere. Least-squares reliuement of 25 reflections measured at room temperature yielded the cell parameters and showed the crystal to belong to the triclinic sy stem. The lattice and crystallographic parameters are listed in Table I. Data were col[coted over the 0 range of 13X) to 27.57 °. Data were collected by the m scan technique ranging in speed from 1.50"/rain the the weakest peaks to 14.65°/rain Ibr the strnngC S I ~ ~tk:' . r ~ " :~C iulensily standards were measured every 47 reflections drawing no degradation of the crystal over tile data collection lime. Data were corrected for absorpliou using the qt scan tedmique on six relleetions covering the 20range. o¢,2,~, SlrtlcO0'c ,w~hllh~l and v¢l#wntcnt tixaulin,ltiou of the dal:t set idenlilied the o'yslal Its belong° iag IO Ihe Iriclinic space group PI {no~ 2 in Ihe lulernalional Tahles l I 131~ A IhrecMmtcnsioual Pallerson syulhe~is ~as call'icd ~LII and the Imsilions of lh0 luoiybdotuul lltOlllS wPre oblahled ill Ihe a~ynlnlclri¢ unit. The i~osilioas of Ihe rcmaiuo ing nond~yd~geu posilions were revealed hy a Fnuricr dil: l~i'ence utap using Ihe heavy meM atom positions, repealed cycles of full-matrix least-squares reliuemenl were carried out until the relinement converged. All non-Ilydlx~geu atoms were relined with aitisotropic temperature factors and hydrogell atoms wt're lixed at calculated positions.
2,4. S,vmhesL~'fCt'Mo:O dSOCNfi,Pr~:~,
3,3, Mo:O dSOCNlioPrbJ,
A small amount of M%{ SOCNt i-Pr): h was placed iu a ce/stal-growing h-shaped cob and ab{~tlt 50 nd of t~duene were ',~uum distilled onto the red powder, Molecular oxy. ~e=, ,ts allowed to blanket the solulkm t't~r sevee,d minute,,,, resulting in ;in instant color cha,tge l~m~ t~d to a greenishbrown, The hosha~d cell wits outgussed and the toluene was alMwM In evaBwate slowly to the other sideof llte vessel, leaving a dark forest-~.t~n crystalline ptx~luct on the sides of the walls, These cod-stalnwere suitablefor single
3.3. I. ('~:v.vm/dam volh,cthm A dark green rectangular crystal ha~,mg |tie approximate dhzlensious of 0.27×0.15×0.12 nun was selecled aud mounted m a 0.5 mm glass capillary and ~ealed in a nitrogen atmt~nphcrc. Ixast-nquar~s relincment a,l| ~,{ rellections taken i'lxml a i~lalion photograph measured ill mum temperature yielded the cell parameler~ and axM phologl'aphs conlirlned the cell ll~ I~long to tile orlhorhombic system. The hulice and cLwsMIographic paramelers are listed in Table 2. Standard centeriug, indexing and dala colleclion programs were used. Data were collected ~wer tile 0 range of 1.90 to 27.5T' using
A.D. {'~ih'amrra ¢>1~l/. /lllol'k~iillh 'il Chlmh'a A, 'm 2h711e9,S't l O I , l i p
IO3
Table I Crystallographic pamineters ltlr Mo:{ SOCN ( i-Pr i: i l " 2THF
Tahle 2 (71~,ntallo~ntphic parameters for Mo ,( ),i S( X'N I i- I~r I. t
Empirical forniula Color Habit Cryshil size ( Innl i Formula weight Temperature I K ) Cr~slal s),slem Space group Unit cell dilllenxiolls
I-rnpirical fuuriula Culor
C .,tl ~_.Mo:N IO+,S~
red oblique parallelepiped o.2{, × O. I ,'4 x o11,~ ~177.1 29312 t liiclinic
Crystal size I rain I Ftlnrlula v.ei~ht Temper'
I0.3961 2 I I 1.473( 3 I I 1.7791 3 ) 75,liJl 2 i I04.34(2 ) I14 27t21 1221.2151
lk i<'l
/J ("! Vohinle I ~ t I /.
4
I
I nllll
1.329 0.7(15
I"i IXI{I I
512 Sielnen~ R 3 m l V Mo K~l I A -. Ii 71117,1 ..%i lraphil¢ 1.81 ill 22.55
iI
11424 Siemens P3 Mo Ktl I A =(L?11173 A i 7raphile I.q|) to 27.57
I)i ffr:ic'tOilleler u~ed Radialitlli 1%/IOllot'hrltnlahlr tl rali~¢ fill dala ¢olicclitlll I I
~ariable'. 1.5il Io 14.65 in .l Ifill m to
t ineii~iired t'~ er) 4"/relk'¢tJ~ui~ - I f , h:;~fl. 1 2 : ~ I ~ I I , -12~.I~- 12 214h7 22214 I h',,,, -II.11283ci; i al'i,,tlrlilioii 171114 ~IHIII l'lllllil'iuiil [rllin II~ ~t'iili ,~i¢lnrn~ lit ~i¢lii¢lls Pt ~11EI .Xl..l%[i I .~hvldliuk, Iqiilli SIII~.IXI.-I;t I ~hl, hhllk, Iqil,l I ~i~'ilil,'ll,, ~III',I,X'II pl' ~. 42 Iiill.illlilli% It'ilM ~qlililL,~ llll I' %t~tll I'], =: ii']I ~ II,ltllll;141 O i riilillt~ ililltk, I u ~ I ! I o:l I,]/i ~ i II il401~1' I: t, ii.llll11411'l. l~'licre P ~ I I,{,' + 21,; <' i/3 R ~- 1l.l).125. IrR ==ll.914714'.i R ~, 11.1167q.wR -- 11.119141~$ I.IIT~ O,IIIMi. {),llllll O.4:1 I) <1,15
Final R Jltdi~'cs i ribs, data ) R indk'es I all data I (lllUdlles~,o t if. I Jt I.argesl iilld nleiili %I~r Dill a-Ill-pln'illiie I¢ r r:llill Liil'l~¢~t dJller¢lit¢ p¢llk lelA'i I.al'Ge~l diffcix'n¢e hllle le/A~l
1.381 I) 8311
l'({14)1) 1
I'i
• ~can lype Scan slk'ed ( '/lit I l •t~Ciill I'lill~ I"! Slilndl.ird relle¢lillii~ Iliik.x rinll2¢~ Ri'll¢clil,ls lrillle¢led Ilidell¢lidt, lil i'elk.cl iOlis ( )lI.wrved r¢licet ions ('ol'rt, t'l Jiin I 'ell I%'lineiiielll I)illa ledllt'lilln ,~1111tllllt" ~lihllii,ll ~I1ii¢Illl L" Itqill¢ inl.lll Mli t't' ~ 'ilp IK'~ r¢lili¢liK, lil liielllild Qutinlil) iniliilili/¢d Exlin¢liiill ¢lll~ll,¢liilli. I I:l)'dl:Ogl'ii iihllli~ Weilliling st'ht'lne
21.45~( 7 15.630t 3 ) 12.63815 l 423812 I
I)ennity I talc. I I M~/lU ~) AhntlrplJlln cue flJcielll
I)ensity I ¢a1¢, I I M~ ! lit' I Abnoipiillli ¢oellJ¢ Jeni I nnn ~l Dil'liaetolnc.lel tined RadialJt~n Mllnilehronl~ihli ~ tl Range Ior dalli t'illk.¢liOli
dark green rectangular paratlelepilx.'d O.27 x C I 5 xll. 12 8140.89 293( 2 ) orlhorhombic Aha2
Hahit
/>i
/,{AI clAI
('>H ~,,Mo:N+OS~
0.~,34
~ C'illl t) pc .l~l~ln ~peed I / inin I gc'Lill fallt2~, i I •Shnldard ",'lle¢lJllii~ Index ralil2~s Ilelle¢ihlns eulle¢lcd hldependenl ielle~lit ins ( )h~el'ved refk,¢l ioils Absorplhin ¢llrrection Cell relin¢lnelil I)ala i%'dli~'ljtlli ~ll
(o
~ari:lhle: 1.5 tt~ 14.65 m ~,~ 0.70 in o~ 3 nleasurede~r) 47 reflections
25h7 qR,., ~: I).[)tlr~' ) 1~1)2 S¢lttJoellllpJrJ¢;ll frtiln I/" ~l.illl,~ ~lelllell~ p?i Si¢lncn~ XI)ISK glllil+Xs xh I ~hehhiek, lilq!ll ,%III{I.XI :lJl I Mwhlliek. Iqq ili ~i¢lllCllS SIiI'.I+XTI I'(' +. 4,2 lilll nllilli% I¢il~l ~iliiiilt.~ I,II I II [)(Ill(till ? ) I+idlli7 ililld¢l u ,-+ I/i,r'l
I,,'i
+ !llll,lll4Pi
+ *ll,lIO(IO#'l,
~,i,ht'lV I 1~ I I ,,' + ~/+L I f I RI ": il,il44,1, ./72 : II ii'/bll4 R I " II,IIVLI2, nR2 °" li litl 17 I .llJfl
Final R ilidiee~ I I :' 2it I I I I l? illtliee~ I ~lll dlila ) (hllittlles~.t~l.lil till I .tll'lJ¢~l and nk, illl .~ I ~r D;il;i-h l-p;.ll;in lelL'r l'illJo I ar~¢sl dillerenu'e peak (e/A') I .iil~¢sl diff¢lent'e htll¢ [etA'l
- 418t14.111124
O,1:1 lLhB3 o 3xJ
3.3.2. Slrm'lure sohtlima and re#nement l:,xmnination of the data ~cl idcnlilied lhe cry~i~l as belonging to Ih¢ t~rihtu'httmhic x p a c e g r o u p A h . 2 I no. 41 in II1¢
Ihe ~o s c a n t e e h l l i q i l e
w i t h il V a l ' y h i g scan i'iit¢ i'iiliTJng I r o l l l
1 . 5 0 ° t I n i n f o r ilie w e a k ~ s t p ¢ i i k s Io 1 4 , 6 5 ° / i i i h l esl p¢liks, T h r e e i l l l ¢ l l s i l y r¢lle¢lions showing
[ o r the SllOllgo
,~liilldards W~l'¢ i n e a s t l r e d eVel'~ 43
no discernible
d¢gradaliOll
o v e r Ih¢ c o l
leeiJon l i m e , I ) a l a Wel'e ¢ o r r c ¢ l e d for a b s o r p l J O l l u s i n g i/r sol.ill illfornliilJon oil six
rell¢clions
¢overhlg
the 2 0 rilllg~.
inlermltionul
Tables)
1131. A t h r e e - d i m e n s i o n a l
Paiter,,,on
s y n t h e s i s w a s L':lri'il2d Out a n d the p o s i t i o n s o f the niolyl~deo 11LIill iltOills W¢l'e o b t a i n e d
in the a s y m m e t r i c
Ullit. B y IIS,Jll~
the h e a v y met:tl a l t ' m p o s i t i o l l S a F o u r i e r d i f f e r e n c e calculated, hydrogen
rgvealing
the p o s i t i o n s
limp was
o f the r e m a i n i n ~
non-
alOlllS, R e p e a l e d c y c l e s o f f L l l l - m a t r i x l e a s t - s q u a r e s
1(1,4
A.D. ('lh,alerra i,t ill. I him'l/l,ni 'a f'himlca Achi 2:671 lOq,~) 101-107
relinement o n F ~ were carried out until the reliiiemeni converged. All non-hydrogen atoms were relined with ani.,~)impic temperalure factors and hydrogen atoms were lixed at calculated positions,
l
4. Results and discussion 4. I. Synthesis und characterization
F
Fig. 2. Stereo packing diagr, un of Mo:( SOCN( i-Pr )~, 1 : 2 T H F .
The reaction between stoiehiometrie amounts of Mo:(O:CCH~)4 and the monothiocarbamate salt. LiSfK'N{ i:Pr);, in ethanol results in a red product lbrmulated to have the elemental coml~isition Mo,I SOCN( i-Pr): I.~ ba~d on elemental analysis and the single-crystal study. The preparation of this Mo( !! ) complex is similar to the methods of Steels et al. 131 and Ricard st al. i 41 for the prepanition of .~veral dinuclear niolybdenum compounds having the general torinula M=,L4, L = S:COEt. SOCPh. S,CNEb). A small quantity of Mo4 SOCN(i-Pr):)4 dissolved in toluene with trace amounts of oxygen afforded a dark green crystalline compound having the composition Mo,O,o I SOCN(i:Pri ~L. The preparation of Ihi~ Mol V ) complex i~ .~imil:ir to the metht~l of Cotton et al. 1141 and Baird and Croll 1151 for the preparation of Mo~OdC~H, NSi4 and Mo~O~( S~CNEt,)~, respectively. A thermal ellipsoid plot of the molecular structure of Mo=,ISOCN(i:Pr)~I~.2THF i~ d&phlyed in Fig. I and a ,~lereo packing diatlram i~ ~hown in Fig, 2, Fhlal illOllliC cooro dhlaie~ lind lelllpcrldure facl,~r,~ are Ii~led in Table 3, Selected bond lenglh~ and Imgle~ I,,¢ listed in Table~ 4 and 5, i%;~!~¢= l i v e l y , l = ~ i i m i i l e d l l i i l l d l i'd d e v i l i l h l n ~ d¢l'i~¢¢d f f o n l Ih¢ It, f i l l . ~qtltl~
,intlly~i~ a p D e a i ~ tn llarciithe~e~
T h e u n i l c e l l i l l IVl~h01 ~ O ( ! N t
' t i l e r c'ach Illtlntlt~r~
ioprl: I,, ~TFIF
¢Onlliin~ oi11
Table 3 Alomic ¢~mrdinal¢~, i x I11~1 and cqtlival¢lll i~oll'~pi¢ dir, placcnlenl c0~efli. ¢ient~, i Jr' × I(t~l lot lkhbt SOCNt i-Prl: I ? 2 T H F Atom
I
Mo S( I 1 ()l I ) ('l II i
I
."
552~! I 1 5116£,~3 t 37591 £~1 4187101
5~145t I t 51(Gt 2 t 291314 t 3-11i516 I
N( I I
.'At)f~t}i S 1
26061 5 I
('l ('I ('i ('t CI
44331 .14531 Iq12t Jlllll 43521
,',1641SI 1274171 f~13114) 2f~t)ll l(ll 322011~ I
121 13i 14t 15i If~t
121 131 121 IJi I3t
I sq
521151 I I f~441114 I 737016 ) 844815 I 8112181 85..11118 I
79881 ~ I 111221h S i
81117 i
71161 ilfll
7
I
I)~5J 1 "7 I
111321118 I 5(~1il I 2 5,~8J( .1 I,I }f~l ? fl7qfll tl
51~3t 5oi 5 i 5,
5~14111 I 21
ill511 o I
Nt 2 t Oi 2 t ('( 21 I Nt 2 i
f'ffv,lli~ ,t I 7f~ 1416t 71,11~I 1 I I I Ill 2~11q I
.15~111 ~ t 5~9491 4 I 4~1~1 7 I 4~1121 ~ I
( '1 ~ I
~tjllnl I I !
III1~ I I ~ i
('l 211 {'i ~4 t I'l ~1
'14741 1.11 Illtllnl I11
JTJ~l I,I I lll~lllqi
71 i l l X (iNfll II i)
(it,l(~i ~ i id14111 ~ i
~}11f,I ?
I 'l ~f,t
~14171 II t Ilil I~1 lit,
11 }=/i Ihtl'l
IIIN4Ol I I i (~i}lllll
71bl!li ,~ t ~ll?(lli
~.h I i
(141 fl I
171 ~ 1 ~lll fll 1i~t % I '141 1 t
CIl~Si f¢1481 lli i 811~51 }11 7~tl! 131
•12~ I i 5411 ) 5ol 3 i 4t~f 5 I 5,'41-11
9~1 ~ I 7111f~ I
('1 171
{h ~Ti ('1JTt 1't Xl't
a
~1'1.12! I } I 1111871 151 ~1211bl~121
f~ I1~1 IIII fi??,ll I 2
I .~qi iI 1 ItIM ,q I
{111151 Ill!
5 t d l t 141
t°17i =#i
' I qtlivalcllt ik~m'npiL , iI ' d~'lallt'd il~,i~ile Ihiid ol tilt" tl~,ct' ill Ihc ~llhl!),Ollilli#~,d I I It'll~lil
Cllli
Tilbl~" -1 I1~ id 11 I~ll ~ I ,\ i liu .llt~l,i Ni I! 'N t i Pi I, t i ' 2<1'1II
T'qu. M u ~ A i I%b~SI2AI
Fig I. lllt~tmal cllip~nid t~Inl ~t lit, qitltltti,c ~1 M~bl S(E'NI i . l l r l . t • 2 T W . Tli¢illlal cllip~fd~ a~v ~ht~u~ al lilt' ~It*:7 Dl~ll~bilii) lc~cl, It)dm.~2t'li ttl~lll~, tl.tl~,.~l ~ h lilllilltkl I{q' elatily.
2llO?~l:,j 2.171~12~
Mo{)¢IA! ~ I b t'l I I !
2,1j2|41 I 74~1Ii~
I'~ II ! NI I ~
1,15?tt4~
N~ I i {'t I 1~
Nlll ('lli~l ( ' q l t ~ ','ll.l! ('l tf~-('~ 17~ ,%121 M , 4 u A I
I~{iX! ISlSII2~ 1,5tt7q I t I 2,471~12t
1't12t ( ' t l 3 t 1 " t ~ 1 l'llt~t S~2t-,('i 21 ! I:~121-('121~
1:|8111~1 1,51S~121 152':,112~ 1.7a,l171 1.2711181
Ni 2 t o-('~ 21~~ Uq21~t.-I'I2Tl i[tt I1 b4.'l 4T~ ('1 21"1-4.'t 3"!~ I
1.48518 t 1.5111t I I ! 1.3ldl 131 I 41~2t
('~ Ill CI ('~
15131 I I ) 1.3741 II I 1+.18111131 1 3~L21
22 t -('t 23 ! I r t . ( ' l IT I ITI ('12|*1 .11 ~-(', 41"1
A,I), Cah'merra el al, t lmu:¢mm'a ('himic. rh'ta 267 ~1918) lot. 107
105
Table 5 Bond angles 1'~) Ior Mo:( SOCN( i-Pr), )a "2THF S( I )-Mo-O( 2 ) OI 2 )-M(r-Mol A ) Ot 2 J-Mt~-O~ IA l
86.57t 14 ) I(X).ITI 12~
S( I I-Mo-SI 2A Mo( A i-Mo-SI 2A
96.n3t S ) 92.37~ 6 ) 103.7121 120,315 } 119.2161
St I I-Mo-Mo~ A I S( I ~-Mt~-OI IAI Mn( A )-Mt~O( IA ) OI 2 I-Mo-S( 2A ) O( I A )-Mo-S( 2A ) C( I I ) - O I I )-Mo(A) S( I ) - e l I I )-N( I ) C( II I-N( I l - e l 13~
88.51 21
Mo-S( I )-el I I S( I I-C~ I I i-O( I ) OII I-C| I I i-NI I ('t I I )-N( I ~-C(16) N{ I )-17~ 13 i-(.'~ 12i C1121-C( 131-C1141 N( I I-C1161-C1171 C121 )-$12 )-Mo( A ) S12)-Ct 21 )-O(2) O121~('121 t-NI 2~
121,616)
C( 13 l-N( I )-C116) N( I )-C( 131-C1141 N( I ~-C( 16)--C(15)
112.9181 113,3(8) I I 1.7(8) 11)3.41 3 ) 120.7171 18.71 f~)
('I 21 )=N( 2 l=,k'l 21~I
21,{~16)
Cq 22 )-('( 23 ~-('{ 24 NI 2 I-('126 l-C( 27 l CI IT)-O( IT~-('(4TI
I 1,818) 12.5181 12.6q 6 ) 10.418 )
C( 15 I-C( 1 6 ) - C ( 1 7 ) M(~()( 2 l-C( 21 I S( 21-C121 )-N[ 21 ('121 J-N( 21-C1231 ('q 231-N121-C1201 N(2 I-C123t-C124j N(21-C(26)-C(25 I ('q 25 ~-C( 26 I-C'[ 27 I ( h IT)~Ct IT) C[ 2T)
n14.lh I I i
('I 2'I')-('(3T)-C'(4T)
Cq I T l-C( 2T )-Cq 3T O( IT l-C( 4T t4"( 3T
III.6(7~ 113.8(71
106.6(I0) 110.2113~
In7 7~ 12
Table ~'~ M*~-IVloboml di~,l:uwe~,h," M J. ~" 21/
Coml~mml
Moq.' I A )
Mo-Mo l A I
RcI.
Mo:t O,('('F, ) a" 2P) Mud S,('OI'I I~" 2TIIF M~d ().('Ph) ,. 21 digl~me i Mo4 S:CPh ! ,. 2'I"I II; l~h~! S~CMe I ~. 2TIIF
2.54,~ 18 ) L705[ I ) 2 6631t~) 2,72717 ) :?712t (~)
2.120! 2 ) 2.1251 I ) 2.11101 I) 2,1301 2 J 2, I~ h I ~
116 I 14 l 1171 17 l I 71
~'enll'nsynmlvlri¢
92,21¢61 167,151 II 1110.33t ] I ) 16"/.119112 ) 86.3~ 2 ) 122.3~4~ 120.5t5) 12{1.1~6~ 118.116~ 112.0~8) 111.3t7) 113.7(8) 121.8(5) 120.6( 6 ) 121,2171 I It~.917) 112.3~8~
i n o l e c u h ; , "|1he M o , ( S O ( ' N ); ~'ore o1' the
n | o l e c u l ¢ pnssrn~es nearly ideal I)fla ~,ylmtlelry. T h e Mrtictare o f the I n n l y b d e n u i n lilnl~olhiocarbziln~.|t¢ ¢ o n ) p l e x i ~, s i m i l : l r
Increasing the strenglh of tl~e metal-axial ligand bond must restlll in the melal-m:.tal bond lenglh. This lel)glhening of Ihe nlelal-lnelal bond is nmximized when Ihe axial Iigand in Very ele(.:lrOll withdrawing and the other ligands are very go(xl electron donors, as in the Moz(O,CCF,}4.2P ), complex reported by Collon and Norman 1161. The sleric and elec° Ironic properties of tile ligands themselves might also lend to Ihe lengthening of the Mo-Mo bonding disu:..,,x A Ihermal ellipsoid plot and a stereo packing diagram of the t|ltflecular sli'tt¢tul'e of MoXid SOCN(ioPr),), are displayed in Fi[~s, 3 and 4. respectively, I;inal atonfic coordinate~ CI6J
to Ihe ¢arboxyhzte ~ol|lpLl|llld~. h a v i l | g Ihc ge||eral f o r l n u l a
M~L,,,21J. The Mo=Mo dislance of 2.112(1) ,~ for Mo~( SOCN(i°Pt') ~L;' 2TIIF i~ ¢OllSiSletll with those lisled in Table O. The subslilulion of the softer base sulfur for oxygen in Ihe houdin~,, ligands shows no signilicam change on the Mo-Mo bond dislance. The Mo-S dislances of 2.481(2) :rod 2.474( 3 ) A in the Mo,( SOCN(i-Pr) ~L;" 2THF comple× do nol signilicantly differ from those of the dilhiocarboxylate compounds or the xa,lthates, which have average Mo-S dis= lances of 2.465( 81 and 2.477( 2 ) ,~. respectively. The MoO distances of 2. 119( 6 ) and 2.130( 5 ) ,~ are also reasonable values to the average Mtv--O distances found in Mo2(Ofl?CF,).;'2Py 1161 (2.116 A) and Mo:(O2CPh).,' 2(digly,ne) 1171 ( 2.107 ,~). The Mo-O(THF) di.,,lancc of 2.690(6) ,'~ could indicate a weak inleraclion belween Ihe molybdenum and tetrahydrofuran. Tlus is generally the case when axial ligands are bound IO a molecule posmssing a very strong M-M quadruple bond. Collon el al. I ]81 have reporled that the auaehmenl of axial ligands Io co,npounds having Ihe general fornmla M2L~ slightly lengthens the M-M bond.
:c31
Fi B. 3 Themlal ellipsoid phil of Ihe slrllcltlr¢ of Mo,()d .~O(*N(i-pr), I,. 'rhernml ellipsoids are shown at the 50r/~ pnd~ability level. Hydrogen arums have becrl olnillcd lor ¢larily.
A,D, ('~dcatPrr++ e! al. / Im,'.+anica Chimica Acla 267 (lO0,e,) I O f 107
I(J~
< N Fig+ 4. Stereo packing diagram ~)t' Mo,O ( SfK"N( l+Prl: I+~ Table ? Atomic cm)rdinate~, ( x I0 +) and equivalent isotropic displacement coefli~'ient,, ( A × I0 ~) for Mo:O+( SO~N( i-R'): )+ Atom
.i
y
"
U,,, "
O( I )
~(XX)
(1
31 ( 2 )
Mo O(21 S O N C(I) (?121 C(A) f(4) C(A) ('10) ('(?) S'
416.1(I) ~889( 2 ) 4309(I) 44.~7( .I ) 4659(3) 44~5(41 4702(5) 4407(~) M$111~)) 47741¢)) ~]4H(~) 41q5(5) 11'169(11
273(I) 361(3) 185|(I) 734( 4 ) 206615) 15211b) 2081)16) ]567()~) 311qt(8) 17,%(~)) 117~(X! I ]q~(~)) + 1144(1)
196(5) = 105217) 370(5) 182g( 7 ) 2426(8) If~l(8) 2183(I0) 2947(12) 2178< 12) ~5201 O) A,~)/~t)(I111 ,I0~0< 111) ~),'-)(~)
34(1) 47( I ) 48(I) 48( I ) 55(2) 45(21 o4(3) t)](4) nTt4) 6014) 8411) I114< 4) ~111
N'
271~4( ,I )
- ?t),~( 5 )
I )~761 (4)
(~412
(~tS) ('l ] ' ) C14'1
273~1 ~) =~?t~(?) ~11)~1~1
t7(13(?) = I~,~4( I11~ - ~=14,~1In)
~142( II1 ]~2112) I,~il( 131
F)1(3 111i,115 11"115
CI0') ('(?')
1'4.1~15 ) 2562(0)
198181 454(.~)
13931131 ](M~)t 11 )
11181,~ 111114
(1
Table 8 Bond length,. ( A ) for Mo,O ;( S(K:NI i-I)r ) : ); Mo-O( 2 ) M()-,,O' M(~S' O=C{ I ) N 4 : ( 21 N-C( 5 ) C( 2 )~('< ,~ ) C( 5 )-('t 6 ) O';C(I') N'=('< 2'1 ('( 2' ) ( ' ( 4' 1 C( 5' )+C( t)' )
1.68915 ) 2.131 ( 51 2.441 ( 2 t 1,252( IO1 1.492{ I I ) 1.4%1131 1.52f)( I ,~ ) 1,531 2 ) 1.27<)( I01 1,457t 13 ) 1,54( 2 ) 1,481 2 )
and temperature facto~ are list~ in Table 7, Selected boml lengths and angles are listed in Tables 8 and q, Estimated standard deviations derived ia)m the least+,,~luaresnnalysis appear in parenthe~s alter each number, Four m)n-centrosynllll~tric molecules occupy the unil cell of Mo.,Od SOCN i i-Pr )., ).+.The general structtm~'of the mol~.'~uleconsists of two dimarted octahedmi sharing a hridgin.~ oxygen ~ ) atom, which g ~ s to I\mu an almo,~tlinear Mo-O~M~) bond having the angle of 1~4.?t4)" A second, terminally bound oxygen (0,) atom along with the two sulfur attmls aM two oxygen atoms th)m the m~mothiocai~tmate ligands c~+nplete tbe octabedral enviromBent about each of the molybdenum atoms, The tenainally bound oxygen atoms
1.8621 ( I I ) 2263( 6 ) 2.4%( 2 ) 1.752(81 1.342( I(11 1,51 ( 2 ) 1.51112 ) 1,74~( q I 1,325( I111 I ,.184112 ) 1,5512 ) 1550,t 14 )
'taM,: o l|olld iu1~lP., I ' i (.111Mu +1),t N(B "Nti lh 1. I + Ill -~1 M~+.(ti I ! (hll, Mo It' Ill I )=Mo <')
III/i. Jl ,|
ih2)
( l t ~ l M o S' O' +Mtt,-S* O! 2 l+Mt)+S O'=M~)-S S'+M~+=S
Itl'.~.ll
( h I F=Mt) S' 0.- M;)+S' O( I o.,M,a,: ~ ()~M~+S 'Moo* (h I ~- M o r a l ('~ 1 t+O+Mo
++)4,'+,)2~8) ;},~.|)( ~ b tjtt,,?3! 5 I 04?(2) I(d,?(4 ~ I(Hk3( 5 t
('i I r N -,('t~ !
12oxt ~)I
O.~('t I ) o N N , ( ' t I J+S N C t 2 )) +('t ,'t I N+('t 51+('~ ? I ('~?} -('i 5~-C161 ('t I' leO'--Mo ('~ I +))-+N' +('t ,~+ ~ O'+CI l'b+N + N ' - ( , t I' b-.s" N ' - ( ' ( 2" ~-o('t V i ('tot' ~ U ~ 5 ' ) - N ' N'+C( 5' b-C( 7" I
12 I,('~t S i
~)L612 t~4,2~2 I ~4,11?t,
(St I )-S=Mo
12(1,5q 8 ,' "l]quWal+llt im,,tr,t)pl¢Ud¢litlmJ a~oBe lhirdol'lhe tru)¢e of|Ix, v~ilhog).t,nalized (~/,)I+lff~,l~l',
~ho=O( I ) Mo-O M(~S S+C( I I N-C( I 1 (7( 2 ) =(7141 C( 5 )+C( 7 ) S'+C( I' ) N'o+C( I'1 N '-CI 5' ) ('( 2' i - ( h ?,' ) ('i ~' i ( ' l ?' )
('( 2 1 N-.('~ ~ ) O-(:'~ I 1.5 N-(,~21 ('14 I~ 1,9181 N - ( ' ( S r ('(+~)
(?t I' )+,S'~Mo ('< I' ). N'-('t 2+
I Ins( ~Ai ??,91 ,~I
('~2').,N' ('(~'l (~'-(,t I + t-S+
N'+(,t 2+ F ( , t a , ~ ('t 4' ~ ,('12' ~ l.'i ]' )
I124~II! 11t),(~( I I I 112,{~1 II11
'M,), t Y
~)? ~(2)
122,q17)
I I I,(+t q ) 112,1tq) 114,q( 12} I(11.+~45 I 1211,?(8 i 122,2(8b
124.3( I12,~( II,LTt 1 I0,7i
71 II~ I0) 8)
have an average M~O, distance of 1.689(5) A, and i)ave considerable multiple bond character a.~discussed by Cotton and Wing 1191. The temfinal oxygens are cis to one another acn+ss the Mo-O-Mo bridge and are directed slighlly away
A . D . C . h ' a l e r m el (~L / h.)r~a)m'(i ('himh u A t t a 26 7 t I ~IVSl I Ol -. 107
Iil7
Table 10 Average l~)nd lengths and angles oI related ctmlpnunds to Mo.,O d SOCNI i-Pr ~: 1,
Mo-O-Mo i ') O,-Mo-O~, t") Mtv-Ob ( A ) Me-S,, ~A ) Mo-S,~ ( ,~ ) O, geomel D'
Me--O-Me ( ~') ()~-Mo.-Ot, ( ° ) Mo-Ob (At Mt)-S,, I t~ ) Me=S,, ( A ) O~ g¢~,),lletry
Mo:O,t S:COE! ), 1221
M,:O,I S:Pt OEt ):l~ 12III
MOO,, S:CN(Pr), h 121 I
17K03 ±4.n6 103.74 ± 2.117 1.862 ± O.(MS 2.702 4- O.01 2.486 + 0.026
linear" 1113.11110, 1.863( 12 ) 2.801 t 5 ) 2.495 ( 9 )
178. I ( 7 ) 102.918) 1.863118 ) 2.6781 5 ) 2.465 ( 14 )
,'is
tra,x
cis
Mo:(),! C.H,NS )~ 1141
Mt).Od 2-SC~H,N-3-SiMe, h 1231
linca~ ~' 105.912 ) 1.853q II 2.3115151 " 2.18515 ) ' I'),(tlz~
linear ~ I05.O( 2 ) 1.8631 I ) 2. Iq9151 2,491112 ) and 2.452t 2 ) ' ( i.~-
Exact value not rept~rted. ~' Mo-N. ( A ). • Me-N,, i A 1, S,, = sulfur Irtm~ It) ()~. S,, nalfar ci,s It) 0,, N,, =' nilrogca Im#,.~ to O,. N,, :: ,,ilroge,i (it h) 0,.
from one another. A t r a . s relationship of terminal oxygen atoms can he fonnd in Mo:OdS:P(OEt)2).t 1201 aad blozOdCsH.,NS)., l l4l, indicating that both the ('is and t m n s arrangements are generally possible. The average O,Mt~Ot, angle 197.512)°) is in good agreement with previously reported valnes. This angle is it result of repulsion between the lone pairs of electrons on the Mo~O bond and the lone pairs on the Mo=O hridging oxygen atom. The n1ononleric nlolybdenum conil)lCx of Mot)z( S:CN (Pr) o:).: 121 I also exhil~ils {111 O-,.Mo. 0 ilolld an~l¢ o f 1()5,7( I )'~, w i t h i n re|lsonllbh.' p l ' o x i n l i l y o f IIl~ 9"],~ ') reporh.'d for llle d i m c r i c lllltlitl~,
II i,~~,if ilitOl't-'xl IO nlllC
t h e t¢l')llhlal o x y g e n ) t h a n the ('Li M o O
thai
lilt.' Moo-Ob l i n d s
II'tltl>; IO
a l o n l are s i g i l i l i c a n l l y Ioll~¢r ( 2,263( 61 di,,,lam:¢ t)f 2, 131
( 5 ) A, T h e iiierca.,¢
oI' tile Me-4) bond/ram' h) the Me4), bonds i.~ a genCl'al phenomenon l'ound lhmoghoul the Mo~Odl.l.).) colno l~)unds. Rehlted bond lengths and angles IO the Me:O,. (SOCN(i-Pr).,)~ compound can be found in Table I0. Tl~e single-crystal struclure oI' Mo2Od SOCN(iopr), ).~ is nnique in the fact thai no other compound in Ibis class has chelating ligands attached through an oxygen atom.
these types o1' compounds have been delennined and arc reported here. References I I I t-.I. Sliclcl. I)rog. Inorg. Chem.. I It.~77 ) 22. 121 T.A. Stcpheuson. I-. Ilatmistcr and G. Wilkinson. J. Clwm. S,,.',. ( 19641 253K I~1 D F..%h.'¢h: lll|tl TI~, ,%tepheI,~ol,. lao, g N u l l ('h¢l|,, I.¢tt,, 9 ( 197=~1 777. 141 I. Rieatd, P, Kara~'ian.idis ,rod R 9v't.ls., htorb! ('hen,. I j ( IqT~,l jlTq, 151 I,. RMud, J. I;stiL',l,le lind I'L Wt'tn.~. J ('heul. Stw. ('h¢ln ( ' 'mmn, 11972 ) ')!X),
Iol I R itmrd, L 1~!4i¢,l,K!'imd R, Weiss, h,or¢ ('he)., 12 t I t.~73) 2 1 ~ 171 F,A Coll.,,, P,II, I=aav~i~k. RII, Ni~.a,,d¢l Jlid J (I, Sekah)v,~,ki~ ~ehl Chem. Seaml,, Set, A. 32 1 19781 66~
I s l F, V¢lht mid J, Zt, biela, J, ll,nl~. N.~'I. ('hem, 4l) t Itrls ) 4~7 191 (;.Z, Ilol~K,. Z, Aa.r~. AIl~, Cheat,, 5? ( 19761 42K I01 S,I.. Hawthor)|¢, A.H Brudzr and R,C. Fay. h,.rt~. Chem, 17 ! p)TN) 2114. I I I A,B. Bri~n.le aud F.A, ('olll)n. luorS. Sylllh., 13 11972 ) 87, 121 L. Mess~rl~. Chem. Rev,. ~18 (Iq~X) 1"129. 131 D, Cou~ouva, is. I)rttg, hmrg, Ch¢ni,. ")6 I I L)70 ) 30 i. 141 I : . A . C . t t o n , P,I-, I:allwil.'k illld J,W, Fitch. It'.)rg, ('he,l|,, 17 I I gTHI 3254.
5. Conclusions Replacemcnl of the ace(ale groups by the )m)nothiocarbamate ligand was shown to form ;icompound having the general formula Moz(SOCN(i-Pr):=h. The dinwric species maintain the original acetale structure ahmg with the shor! Me=Me bond length, indicating the strong quadruple hond= ing between molyhdenum alon|s. This dimeric compound was also shown It) undergo a reaction with molecul',u" oxygen to form Mo~()d SOCN( i-Pr)2 )a. Crystal structures of both
1151 I)M, Baird and S,D, (?roll. Polyhedr.lL S (19)46) 1931, 1161 F.A. Cotton and J.(;. Nol"nlaI,. J, All1. ('l'ten,. So¢. 'M ( lt172 ) 51~.J7. I 171 I).M. Collins. F.A. (,otlo,I alid C, A, Murlll., I,lor~. Ch¢,ll.. 15 t 1976 ) 2¢150. I INI F.A. ('tilt(m. M.W. Iixtille and I..I}. (;age. I,It),~d. Chem.. 17 (197M) 172. 19I F.A.C.tt,n aqd R.M. Wing. In,r!:. Chem. 4 i ItU)S ) x67. 2nl J.R. Knox a,ld C K, Protlt. Acla Crystalh)gr.. Sect. B. 25 ( Iq69 ) 2281. 211 I., Ricard. J. l'Mienne aud R, Web, s. J. Cootd. Chem., 3 ( 1974 ) 217. 221 A.II. Blake, F.A. Cotton a,,d J.S. Wood. J. A,11. Che,n. See., 86 ( lqbJ, ) 3O24. 23l F. Bh)ck. M. (;¢r,a,). II, Kang. G. Oh)ri-Okai aim J. Kuhich). Im),~ Cllenl.. 30 ( 19111) 17311-1747.