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J. CHEM. SOC. DALTON TRANS. 1993 35Metallaheteroborane Chemistry. Part 12.' Synthesis ofCationic Metalla heteroboranes [2-L-2- ( PPh,)-c/oso-2,1-PdTeB,,H,( PPh,)] [ BF,]; Molecular Structures of theCompounds with L = H.0 or CotJames P. Sheehan,a Trevor R. Spalding,*Sa George Ferguson,*Pb John F. Gallagher,bBranko Kaitnerb and John D. KennedyCa Chemistry Department, University College, Cork, IrelandChemistry Department, University of Guelph, Guelph, Ontario N I G 2 W I , CanadaSchool of Chemistry, University of Leeds, Leeds LS2 9JT, UKThe reaction of Ag[BF,] and [2-1-2-(PPh3)-c/oso-2,1 -PdTeB,,H,(PPh,)] 1 in toluene for 30 min at roomtemperature and subsequent isolation of the product under aerobic conditions afforded [2- (H,O) -2-(PPh,) -c/oso-2,1 -PdTeB,,H,( PPh,)] [ BF,] 2 in excellent yield.This complex has been characterised by(I R and l1 B N M R ) spectroscopy and X-ray crystallography. Crystals of 2*0.89CH2C12 are monoclinic, spacegroup P2,/c, with cell dimensions a = 14.073(3), b = 15.640(2), c = 20.262(6) 8, and p = 94.80(2)". Afinal R factor of 0.038 was calculated for 5595 observed reflections. The Pd-OH, distance is 2.208(4) 8,and Pd-P(l) is 2.3544(14) 8,. Cage interatomic distances include Pd-Te 2.6958(6) and ranges for Pd-Bof 2.1 92(6)-2.299(6) and Te-B of 2.287(6)-2.403(6) A. Theexo-cage B(7)-P(2) distance is 1.950(6) 8,.The water molecule in 2 can be displaced by a variety of ligands to produce the cationic pallada-telluraborane complexes [2-L-2-(PPh3)-c/oso-2,1 -PdTeB,,H,(PPh,)] [BF,] [L = CO, CNBu', CNC,H,,,NCMe, MeCH (Ph) NH,, OC,H, or SC,H,) in yields ranging from 39 to 93%.Reaction between 2 and a ten-fold excess of PMe,Ph affords [2,2- (PMe,Ph),-c/oso-2,1 -PdTeB,,H,( PPh,)] [BF,] in 75% yield. Allcomplexes have been characterised spectroscopically (IR and lrB NMR) and in the case of [2-(C0)-2-(PPh,) -c/oso-2,1 -PdTeB,,H,( PPh,)] [BF,] 3 by X-ray crystallography. The 3.C6H,Me solvate crystallisesin the monoclinic space group P2Jc with Z = 4, a = 14.509(3), b = 10.732(1), c = 31.377(8) A and= 97.49(2)". The final R factor of 0.054 was calculated from 5439 observed reflections. Principalinteratomic distances include Pd-Te 2.6897(9), Pd-B 2.1 95(10)-2.307(9), Te-B 2.262(11)-2.389(9),Pd-P(2) 2.367(2), B(ll)-P(l) 1.941 (9) and Pd-C(1) 2.003(9) A.Virtually all the metallaboranes and metallaheteroboraneswhich have been described are either neutral or anionic.2 Thevery few cationic compounds which are known include nido-[Fe( CO),( B ,H9)] + (ref.2) and [ 1 -(q 5-C5H ,)-7-(C,H ,N)-closo- 1,2,4-CoC2B,H,] + ., The former was unstable above- 30 "C and the latter decomposed within a few hours at roomtemperature when dissolved in polar solvents. The preparationof these compounds involved either the protonation of theborane cage or the removal of a hydride ion from a p-B-H-Mfragment.4 An alternative approach to cationic compounds wasreported with the electrochemical oxidation of [commo-3,3'-Fe{ 3,1,2-FeC,B9H,o(SEt,)},].5 However, the iron(m) complexcation, isolated as the perchlorate salt, defied all attempts topurify it and work on this complex ceased. More recently,Kang et al.reported the synthesis of [commo-3,3'-Co(4-[4-(MeC0,)C,H4N]-3,1,2-CoC2B9Hlo}2JCl from the reactionbetween CoCl , and [nido-9-(4-( MeCO,)C, H4N} -7,8-C2B,-Hll]- in thf. Since the chloride complex was relativelyunstable, a salt was prepared with the [nido-7,8-C,B,H1,] -anion. Both these compounds were characterised by spectro-scopic methods but no crystallographic studies were reported.One of the conclusions of this study was that the instability ofthe cobaltacarborane cation was due to the presence of thepositive charge.6In continuation of our study of transition-metal complexes ofheteroborane ligands,' we now report the use of metal-centredchemistry to synthesise a series of nine, air-stable, cationict Supplementary data available: see instructions for Authors, J.Chem.SOC., Dalton Trans., 1993, Issue 1, pp. xxiii-xxviii.metallaheteroboranes with the general formula [2-L-2-(PPh3)-closo-2,1-PdTeB,,H,(PPh3)][BF4] where L = H,O, CO,Bu'NC, C6H lNC, MeCN, MeCH(Ph)NH,, tetrahydrothio-phene (tht), or tetrahydrofuran (thf), compounds 2-9 and[2,2-(PMe2Ph),-closo-2,1 -PdTeB oH9(PPh3)][BF4] 10. Allthese products were characterised by analytical and spectro-scopic data. Generally in this paper we describe the 7-(PPh,)enantiomer for convenience; both 7 and 11 enantiomers arepresent in the racemic products.Prior to this report, only two mononuclear palladium com-plexes containing Pd-OH, moieties had been structurallycharacterised, namely, aqua(benzo[h]quinoline)[2-(dimethyl-aminomethy1)phenyl-N]palladium(~~) perchlorate, [Pd(bquin)-(dmp)(H,O)][ClO,] 11 ' and aqua( l-methyl-2,2'-bipyridin-3-ylium-~C~,N ')(nitrate-icO)palladium(rr) perchlorate mono-hydrate, [ PdL'(H,O)(ONO,)] [C104]*H,0 12.Furthermore,structural studies of mononuclear Pd(C0) complexes have beenreported only very recently, the species concerned being [Pd(q3-C4H7)(SnC13)(CO)] and the anionic complexes [PdX,(CO)] -(X = C1 or Br)." The molecular structures of the aqua andcarbonyl complexes described in the present work, [2-(H20)-2-(PPh3)-cl~~~-2,1-PdTeB,,H,(PPh,)]~BF,1 2 and [2-(C0)-2-(PPh3)-closo-2,1 -PdTeB oH9(PPh3)][BF4] 3, were determinedusing X-ray crystallography.Results and DiscussionThe reaction between equimolar amounts of Cs[nidu-7-TeBl0-H,,] and [PdI,(PPh,),] in refluxing toluene for 17 h affords[2-I-2-(PPh3)-closo-2, 1 -PdTeB , oH9(PPh,)] 1 in excellen36 J.CHEM. SOC. DALTON TRANS. 1993[7-TeB,,H, '3- + [PdI,(PPh,),] -*[2-1-2-( PPh,)-2,l -PdTeB ,H9(PPh3)]+ I - + H, (1) 1yield (95.473, reaction ( 1).6 When 1 was allowed to react withAg[BF,] in toluene for 30 min, with the products beingseparated and purified under aerobic conditions, the greenaquapalladium complex [2-(H,O)-2-( PPh,)-closo-2, 1 -PdTe-B,,H,(PPh,)][BF,] 2 was isolated in excellent yield (94.3%),reaction (2).1 + Ag[BF,] toluene-water +[2-(H20)-2-(PPh3)-2,1 -PdTeB ,H9(PPh3)] [BF,]+ AgI (2) 2Initial characterisation of compound 2 by infrared and 'H, ' 'B and ,'P NMR spectroscopies suggested the presence of theaqua ligand, the tetrafluoroborate ion, the B-PPh, unit and thecfoso nature of the PdTeB,, cage.Absorptions were observedin the infrared regions associated with 0-H (at 3395 and1605 cm-'), B-H (at 2540 cm-') and B-F (1094 cm-') bonds aswell as with the PPh, ligand. The 128 MHz "B-{ 'H} and400 MHz 'H-{ "B) NMR spectra showed nine BH units whichwere correlated using 'H-{ "B(selective)} experiments, Table 1.This Table also contains data from [2-C1-2-(PPh3)-cZoso-2, 1 -PdTeB,,H,(PPh,)] 13 and [2,2-(PPh3),-cfoso-2,l-PdTe-Bl,Hlo] 14.' The assignments given in Table 1 were based onsimilarities in chemical shifts and peak widths with data from[2-C1-2-( PPh,)-cfoso-2, 1 -PdTeB oH9( PPh,)] and relatedcompounds.' Additional data from P NMR spectroscopyconfirmed the presence of a B-PPh, unit with 1J(31P-"B)133 Hz, Table 1.The 'H, I'B and 31P chemical shifts andcoupling constant parameters for the cationic cluster 2 andneutral clusters 13 and 14 are remarkably similar which stronglysuggests closely similar gross electronic structures of the closocages. As well as the single BP and the nine BH signals observedin the ' 'B NMR spectrum of 2, there was a very sharp signal ofunit relative intensity due to the [BF,]- anion at 6 - 1.1.Owing to the availability of good-quality crystals of com-pound 2 which were suitable for X-ray analysis, and the notablelack of structural data on aquapalladium complexes, we decidedto determine the solid-state molecular structure of 2.A view ofthe 7-PPh3 enantiomer of the cation is shown in Fig. 1 andTable 2 lists selected interatomic distances and angles in thiscation. Overall, the cage structure is typical of cZoso twelve-atomMXB , clusters.'.' I-' A notable feature of the cage geometryis the almost symmetrical bonding of the palladium atom tothe TeB, face of the TeB,, ligand. The Pd-B(7) distance is2.289(6) A, slightly shorter than Pd-B(3) of 2.299(6) A and,likewise, Pd-B(11) [2.192(6) A] is slightly shorter than Pd-B(6)[2.197(6) A]. The Pd-Te distance is 2.6958(6) A. The ranges ofthe cage interatomic Te-B and B-B distances are 2.287(6)-2.403(6) 8, and 1.737(9)-1.924( 10) A respectively.These aresimilar to those observed in other PdTeB,, clusters.' The exo-cage B-P bond length is 1.950(6) A.The Pd-OH2 bond length of 2.208(4) A in compound 2 isessentially the same as that of 2.20(1) 8, previously reported in[Pd(bquin)(drnp)(H,O)][ClO,] 11.' These bonds are longerthan that of 2.132(3) A observed in [PdL'(H,O)(ONO,)]-[CIO,]*H,O 12.* The Pd-OH, distance in 2 may also be com-pared to the Pd-OH distance of 1.966(3) A in [Pd(terpy)-(OH)][ClO,]~H,O (terpy = 2,2': 6',2"-terpyridine),14 or thePd-0,CMe distance of 2.121(3) A in the neutral, monodentateacetate-containing cluster, [2-(0,CMe)-2-(PPh3)-cfoso-2,1-PdTeB,,H,(PPh,)] 15, which is closely related to 2.6The water molecule in compound 2 is easily displaced byother Lewis bases such as CO, isocyanides, acetonitrile, amines,phosphines, ethers and thioethers to afford the cationic com-plexes 3-10, Scheme 1.At room temperature, compounds 2 andC43)bFig. 1 General view of the cation of the 7-PPh3 enantiomer of thecomplex [2-(H,0)-2-(PPh3)-cloaso-2, 1-PdTeB ,H,(PPh,)][BF,] 2showing the numbering scheme[2-L-2-( PPh,)-closo-2, 1 -PdTeB ,H,(PPh,)] [BF,](iHiii) 3-92 /( i o ) \ L[2,2-( PMe,Ph)-closo-2,1 -PdTeB, ,H9(PPh3)][BF4]10Scheme 1 (i) L = CO, toluene, 5 min, yield 39% (ii) L = Bu'NC,C,H,,NC, MeCH(Ph)NH, or C,H,S, 2:L ratio 1 : 1, CH,Cl,, 30 min,yields 85,93,42 and 87% respectively; (iii) L = MeCN or thf, 2: L ratio1 : 1O00, CH,Cl,, 30 min, yields 90 and 93% respectively; compoundnumbering sequence L = CO 3, Bu'NC 4, C,H,,NC 5, MeCN 6,MeCH(Ph)NH, 7, tetrahydrothiophene 8 or thf 9 (iu) L = PMe,Ph,2: L ratio 1 : 1 1 , CH,CI,, 30 min, yield 75%3-10 are generally air- and water-stable as well as being stable inpolar and non-polar solvents.The crimson carbonyl compound3, which is the least stable of the compounds discussed here, isthe exception to this generalisation. It evolves CO very slowly atroom temperature. All compounds 3-10 were characterised byelemental analysis together with infrared and "B-{ 'H} NMRspectroscopies. The infrared spectra showed strong absorption-band maxima corresponding to BH vibrations in the region2570-2510 cm-' and to BF vibrations in the region 1100-lo00 cm-' which were centred around ca.1070 cm-'. Also, therewere specific absorption bands associated with each ligand L(see Experimental section for details).Measured "B and "B-{ 'H} NMR data (CD,Cl, at 294-298 K) showed eleven boron atoms present in all compounds3-10 with some overlapping of peaks even in spectra recorded atthe "B frequency of 128 MHz. The B-H/B-X signals were inthe 6(' 'B) range from ca. + 19 to ca. -21 and grouped withan intensity ratio of l:(l:l):(l:l):l:l:(l:l):l:l. In each"B-{'H) spectrum there was one signal of unit intensitybetween 6 +9 and +11.5 coupled to ,'P, [1J(31P-"B)130 & 10 Hz] and one signal of unit intensity due to [BF,]- at6 - 1.2 0.3. This latter signal is notably very much sharperthan the others. The "B-{'H}, 'H-{"B} and 31P NMR datafor the compounds with L = Bu'NC 4, tht 8 and [2,2-(PMe,Ph),-closo-2,1 -PdTeB,,H,(PPh,)][BF,] 10 are listed inTable 1.The assignments were made in the same way as for 2.The NMR spectra are remarkably similar (Fig. 2) and confirmthat all the compounds 2-10 are mutually analogous.The palladium carbonyl complex, [2-(CO)-2-(PPh3)-closo-2,l -PdTeBl,H,(PPh,)][BF4J 3 afforded crystals from tolueneJ. CHEM. SOC. DALTON TRANS. 1993 37Table 1 Measured NMR parameters for [2-L-2-(PPh,)-closo-2,1-PdTeBl,H,(PPh,)][BF4] (L = H 2 0 2, Bu'NC 4 or C,H,S 8, [2,2-(PMe,Ph),-c*lo.so-2,1 -PdTeB ,H,( PPh,)][BF,] 10, [2-C1-2-(PPh3)-cfoso-2, 1 -PdTeB oH9( PPh,)] 13 and [2,2-( PPh,),-closo-2,1 -PdTeB, ,H ,] 14 in CD2C12solution at 294-297 K2 b 4' 8* 10 = 13I 14Assignment a 6(' B)g(12) + 18.8(7-1 1) ca.+ 10.8 + 10.9(9) + 6.0(3,6) + 4.5ca. - 1.5(455) ca. -9.4- 12.3(&lo) - 19.1- 20.76('H)h+ 5.42 + 3.74P sub. + 5.01 + 2.61 + 2.33 + 2.80+3.12 + 1.83 + 1.646("B)g+ 19.2 + 13.0 + 9.7+8.1ca. +6.5ca. -9.0ca. - 1 1.0- 4.8- 16.1- 18.36('H)h+ 5.45 + 3.85P sub.+5.13 + 2.79 + 2.33+ 2.98 + 3.25 + 2.30+ 1.886( 1 1 B)g+ 18.6ca. + 12.0 + 11.4 + 7.7ca. +9.0-5.1ca. - 10.0ca. - 10.0- 16.4- 18.46('H)h+ 5.45 + 3.39P sub. + 5.00 + 3.27 + 1.78 + 2.84 + 3.36+2.16 + 1.736("B)9+ 19.0 + 10.8 + 7.2 + 8.0 + 6.5- 5.4- 8.7- 10.3- 17.1- 19.16('H)h+ 5.32 + 4.07P sub. + 5.05 + 2.90 + 1.82+3.16 + 3.42 + 2.33 + 1.886("B)9+ 18.0 + 10.5 + 9.2 + 3.5 + 6.0- 5.0- 10.7- 10.0- 19.6-21.96('H)h 6("B)B 6('H)h+4.96 +23.2 +5.74P sub.+ 16.8 +4.90 + 3.40+4.73 +9.4 +4.96+2.79 +3.4' +1.96 + 2.01+3.18 -11.0 +2.76 + 2.79+ 1.47+ 1.70 -18.4 +1.58On the basis of relative intensities together with shielding and linewidth parallels with previously reported analogues (see ref. 6 and Fig. 2).b6(31P) +30.5 (Pd) and ca. +7.1 (B) ['J(3'P-"B) 133 i- 10 Hz]; 6('H) +2.62 (br, H20); 6("B) -1.1 (BF,-). '6(3'P) +28.5 (Pd) and + 10.8 (B) P-' B) 128 f 10 Hz]; 6('H) + 1.01 (Bu'NC); 6(' 'B) -0.9 (BF,-).' S(,lP) + 34.7 (Pd) and ca. +9.4(B) ['J(31P-' 'B) 133 f 10 Hz].[d. MeP,, 2J(31Pc-1H) 9.6, 3 HI, +0.84 [d, MeP,, 2J(31P,-'H) 9.6 Hz, 3 HI; 6('H) of PMe groups related to S(,'P) by 1H-(31P) experiments;S("B) - 1.0 (BF,-).IS(,'P) +31.2 (Pd) and +11.4 (B) [1J(3'P-"B) 135 Hz].~ "6("B) f0.5 ppm to high frequency (low field) of BF,*OEt,.f0.05 Hz to high frequency (low field) of SiMe,; 'H resonances were related to directly bound B positions by 'H-{' 'B(se1ective)) spectroscopy.The 'B resonance lines are substantially broader (i.e. 300-400 Hz) than the other lines (< ca. 200 Hz).e6(31P)A +10.2 (B) ['J(31p-'1B) 126 f 101, 6(3'P)B [d, 2J(31PB-31PC) 46.5 Hz], 6(,'P), -7.5 (d of d, Pd) [2J(31PB-31PC) 46.5 and3J(31PA-31PC) 7.0 Hz]; 6('H) +7.8-+7.0 (PhP), +1.74 [d, MePB, 2J(31pB-'H) 10.0, 3 HI, +1.72 [d, MeP,, 2J(3'PB-'H) 10.0, 3H], +0.92Table 2 Selected interatomic distances (A) and angles (") in the cation [2-(H20)-2,7-(PPh,)2-closo-2,1-PdTeBl,H9] + of compound 2Pd-TePd-P( 1)Pd-O( W)Pd-B(3)Pd-B(6)Pd-B(7)Pd-B( 1 1)Te-B( 3)Te-B(4)Te-B( 5)P( 1 )-Pd-O( W)Te-Pd-B( 3)Te-Pd-B( 6)B( 3)-Pd-B( 7)B(6)-Pd-B( 1 1 )B( 7)-Pd-B( 1 1)Pd-Te-B(3)Pd-Te-B(6)B( 3tTe-B(4)B(4)-Te-B( 5)B( 5)-Te-B( 6)Te-B(3)-B(4)Pd-B(3)-B( 7)2.6958(6)2.3544( 14)2.208(4)2.299(6)2.197(6)2.289(6)2.192(6)2.386(6)2.288(7)2.287(6)94.22( 11)56.41(16)46.65(21)51.67(23)46.53( 2 1 )53.37( 14)50.65( 14)48.5 1 (23)48.6(3)48.4(3)63.1(3)66.4(3)57.75( 17)1.737(9)1.9 1 3( 8)1.763(8)1.772(8)1.763(8)1.808(9)1.794(9)1.797(10)1.764(8)1.788(8)59.0(3)61.2(3)60.2(3)58.6(4)59.3(4)59.7(4)60.3(3)59.5(4)65.7(3)59.3(4)59.8( 3)64.3(3)59.7(3)2.403(6)1.922(9)1.8 17(8)1.764(9)1.882(11)1.763(10)1.766( 1 1)1.924( 10)1.739( 11)1.76 1 (10)56.9(3)59.0(3)65.7(3)57.0(3)5 6.8 (4)61.4(4)69.0( 3)58.2(4)56.0(4)62.7(3)57.2(4)58.5(3)63.9(3)1.768(9)1.772(9)1.950(6)1.822(5)1.830( 5 )1.823(5)1.808(5)1.81 l(5)1.808(5)B( 10)-B( 1 1)-B( 12) 59.6(4)B(7)-B(12)-B(8) 59.4(3)Pd-P( 1 )-C( 1 1) 109.26( 16)Pd-P(1)-C(21) 1 1 8.12( 16)Pd-P(1)-C(31) 113.19(17)B(7)-P(2)-C(41) 113.09(24)B(7)-P(2)-C(51) 11 1.57(23)B(7)-P(2)-C(61) 11 1.29(23)Pd-B(7tP( 2) 1 16.0(3)B(8)-B(7)-P(2) 114.6(4)B(3)-B(7)-P(2) 118.0(3)B(l 1)-B(7)-P(2) 125.1(4)B( 12)-B(7)-P(2) 1 19.3(4)light petroleum solution which were suitable for X-ray analysis.Table 3 gives selected interatomic distances and angles in the11-PPh, enantiomer of the cation of 3 and the molecularstructure of this cation is shown in Fig.3. Compound 3 isthe first cationic monopalladium carbonyl complex to bestructurally characterised. Previously, the neutral complex[Pd(q3-C,H,)(SnC13)(CO)] and the anionic species [PdX,-(CO)] - (X = C1 or Br) l o had been reported. The palladium-carbon distance in 3 is 2.003(9) 8, which is longer than thedistances in either the ally1 complex, 1.947(11) A, or the anions,1.87(1) and 1.87(3) A for X = C1 and Br respectively. Both theneutral and anionic complexes are unstable under aerobiccondition^.^*'^ It is not clear why the relatively weak Pd-CObond in 3 appears to be more stable to aerial oxidation andthermal decomposition than the Pd-CO bonds in the neutraland anionic complexes.It is possible that the combined bulk ofthe telluraborane cage and the triphenylphosphine ligands issufficient to inhibit the oxidation reaction effectively, but it isdifficult to see why the thermal decomposition reaction is alsoinhibited in 3 compared with the other palladium carbonylcomplexes.The integrity of the twelve-vertex PdTeB,, cage whichwas present in the original reagent, [2-I-2-(PPh3)-cfoso-2,1-PdTeB,,H,(PPh,)] 1, is retained in the cation of 3, Fig. 2.In general, the cage interatomic distances in 2 and 3 areremarkably similar and close to those in the neutral species[2-(02CMe)-2-(PPh,)-cfo.so-2, 1-PdTeB , oHg(PPh,)] 15 and[2,2-(PMe,Ph)2-cfoso-271-PdTeBloHlo] 16.' The major dif-ferences between these compounds are that: (i) the Pd-Tedistance in 2,2.6958(6) A, is significantly longer than in 3 or 15which are the same within experimental error at 2.6897(9) and2.6903(4) A respectively, whereas that in 16 is significantlyshorter at 2.6833(2) A; (ii) the ranges of B-B distances in 2 and 3of 1.737(9)-1.924(10) and 1.744(15k1.929(14) A are very simila38+2 -5- T- z+4 -6("B)+?O , +;o , p , -;o .-?O ,J. CHEM. SOC. DALTON TRANS. 199311+60 1 I Ill I 1 1 I IA 1 I / / y I I ll / IV \ \Ill I v I \I I \ / n \ \O \ l \ ) i \ v I\I - , .1 ' 1 . 1 ' +20 +10 0 -10 -206("B)Fig. 2 Cluster "B and 'H NMR data for the neutral compound 13(O), for the tetrafluoroborate salts of the cationic species [2-L-2-(PPh,)-closo-2,1-PdTeBloH,(PPh,)-7]+ where L = H,O (complex 2,0), C,H,S (8, V ) or Bu'NC (4, A), and for complex 10 (0).The topdiagram is a plot of 6(' H) uersus 6( ' ' B) for the individual BH clusterunits, and the bottom diagrams are stick representations of the "Bchemical shifts, with lines drawn to show the equivalent positions for thevarious speciesand slightly smaller than the ranges in 15 and 16 which are1.753(7)-1.978(7) and 1.733(5)-1.940(4) 8, respectively; (iii) thePd-B distances which are 'cis' to the phosphine in 2, 2.192(6)and 2.197(6) 8, respectively, and 3, 2.195(10) and 2.282(10) Arespectively, are shorter than those which are 'trans' to thephosphine, 2.289(6) and 2.299(6) 8, in 2, and 2.290(9) and2.307(9) A in 3 respectively; this is also the case in 15; (iu) theB-P distances in 2,3 and 15 are the same within experimentalerror, at 1.950(6), 1.94 l(9) and 1.942(4) 8, respectively; (u) thePd-P distance in 3, 2.3673(21) 8, is significantly longer thanthose in 2 and 15 which are essentially the same at 2.3544( 14)and 2.355( 1) 8, respectively.Comments on the Preparation of Cationic Metallahetero-boranes.-The route to the synthesis of the metallaheteroboranecations described in this paper was facilitated by the initial high-yield synthesis of a metal halide-containing complex i.e.[2-I-2-(PPh,)-closo-2,1-PdTeB,,H,(PPh3)] 1.' In Part 11 of thisseries' we demonstrated that 1 was produced as the soleproduct of the reaction between trans-[PdI,(PPh,),] and[nido-7-TeBloH, '1- when the reaction was carried out inrefluxing toluene solution, reaction (1).Under those conditionsthe palladium reagent is thought to retain the trans stereo-chemistry. By contrast, under other conditions, for example ifthe solvent was thf, the palladium complex, say [PdCl,(PPh,),],and the reaction temperature ambient, the palladium reagentexists as a mixture of cis and trans isomers. In this case, the cisFig. 3 General view of the cation of the ll-PPh, enantiomer ofthe complex [2-(C0)-2-( PPh,)-closo-2, 1 -PdTeB oH9(PPh3)] [ BF,] 3showing the numbering schemeisomer is thought to react faster than the trans isomer affording[2,2-(PPh,),-closo-2,l-PdTeBloHlo] 14 as the only isolablepalladatelluraborane.We anticipate that the subsequent step which convertscompound 1 into 2 may be of general use in the synthesis ofcationic metallaheteroboranes, although it is possible that asuitable ligand may have to be added immediately after theaddition of the silver salt to stabilise the cationic products,reaction (3).Work is currently in hand which aims to use the[cluster (M-X)] ( i ) +(:: (ix-) + [cluster (M-L)] -t. (3)principle embodied in reaction (3) to synthesise air-stablemetalla-borane and -carborane cations and to extend thenumber of metallaheteroborane cations known.ExperimentalGeneral.-All preparative experiments and recry stallisationswere carried out in an inert atmosphere. The compound [2-I-2-(PPh,)-closo-2,1-PdTeBl0H,(PPh,)] 1 was prepared aspreviously described.' Infrared spectra were recorded as KBrdiscs on Perkin Elmer 682 or Mattson Polaris FTIRspectrometers, NMR spectra with the techniques described inearlier parts of this series.',' ' - 1 3 Data in Table 1 were obtainedwith a Bruker AM400 instrument and remaining data wereobtained with a JEOL 270GSX spectrometer. Chemical shifts(6) are quoted to low frequency (high field) of E 100 MHz for'H, E 32.083 971 MHz for "B (nominally F,B-OEt, inCD,Cl,) and E 40.480730 MHz for ,'P (nominally 85%H3PO4); peak shapes are designated as vsh (very sharp),sh (sharp), br (broad) or vbr (very broad).Reaction of [2-I-2-(PPh3)-closo-2,1-PdTeB oHg(PPh3)] 1with Ag[BF,].-A suspension of AgCBF,] (0.081 g, 0.414 mmol)in toluene (20 cm3) was added to a solution of [2-I-2-(PPh3)-closo-2,l-PdTeBloH9(PPh,)] 1 (0.415 g, 0.414 mmol) in toluene(100 cm3).The solution, which initially was dark green,immediately lightened and a yellow precipitate formed. Afterstirring the mixture at room temperature for 30 min, it wasfiltered. The solution was collected and the solvent removedunder reduced pressure (rotary evaporator, 35 "C). Recrystallis-ation from CH,Cl,-heptane (1 : 1, 30 cm3) afforded greencrystalline blocks of [2-(H,O)-2-(PPh3)-closo-2,1-PdTeB, oH9-(PPh ,)I [ BF4]*0. 89CH ,C1 ,, 2-0.89CH ,C1 (0.38 3 g, 94.3%)(Found: C, 41.60; H, 4.25. C36H41B1 ,F,OP,PdTe~0.89CH2C1J. CHEM. SOC. DALTON TRANS. 1993 39Table 3 Selected interatomic distances (A) and angles (") in the cation [2-(C0)-2,1 l-(PPh,),-claso-2,1-PdTeBloH9]+ of compound 3Pd-TePd-P( 2)Pd-C( 1 )Pd-B( 3)Pd-B(6)Pd-B( 7)Pd-B( 1 I )Te-B( 3)Te-B( 4)Te-B( 5)P( 2)-Pd-C( 1 )Te-Pd-B( 3)Te-Pd-B( 6)B( 3)-Pd-B( 7)B(6)-Pd-B( 1 1 )B( 7)-Pd-B( 1 I )Pd-Te-B( 3)Pd-Te-B( 6)B( 3)-Te-B(4)B(4)-Te-B( 5)B( 5)-Te-B( 6)Te-B( 3)-B(4)Pd-B( 3)-B( 7)B(4)-B( 3)-B( 8)2.6897(9)2.3673(21)2.003(9)2.282( 10)2.307( 9)2.195( 10)2.290(9)2.338( 11)2.285( 12)2.262( 11)9 2 3 3)55.4(3)56.51(22)49.9(4)46.8(3)47.2(3)53.43(23)53.64(2 1)48.9(3)48.7(4)48.9(3)64.1(5)62.7(4)58.6( 6)B(8)-B(7kB( 12)B( 1 1 )-B( 7)-B( 1 2)B(4tB(8)-B(9)B(9)-B(8)-B( 12)B(5)-B(9>-B( 10)B( 8)-B(9)-B( 12)B( lO)-B(9)-B( 12)B(6)-B( 10)-B( 1 1)B(9)-B( 10)-B( 12)B( 1 1)-B( 10)-B( 12)Pd-B( 1 1)-B(6)B(7)-B( 1 I)-B( 12)B( 10)-B( 1 1 )-B( 12)B(7)-B( 12)-B(8)1.787( 13)1.825( 13)I .79 1 ( 14)1.79 1 ( 13)1.828(14)1.791(14)1.796( 15)1.762( 14)1.770( 12)60.0(5)58.0(6)58.3(5)60.2(6)59.8( 6)59.8( 6)61.7(5)59.1(6)60.3(5)67.1(4)60.1(5)60.0( 5)60.0( 5)1.797( 13)5935)2.389(9)1.9 1 5( 14)1.889( 13)1.744(15)1.876(16)1.795( 15)1.756( 15)1.929( 14)1.788( 16)1.797( 14)58.9(5)65.0(5)56.0(5)58.9(6)61.9(6)69.0(4)57.2(6)57.2(5)60.1(6)66.1(4)5 8.7( 5)56.5(5)57.7(5)1.774( 14)1.78 1( 14)1.941 (9)1.01 9( 15)1.808(9)1.8 16(8)1.816(9)1.839(8)1.8 18(9)1.80 1(9)177.0( 1)114.1(3)1 12.0( 3)1 17.4(3)11 1.8(4)114.8(4)1 1 1.6(4)1 18.0(4)1 2 1.3( 6)125.0(5)114.2(5)1 15.8(6)requires C, 41.95; H, 4.10%).IR: v,,, 3395m (br) (H,O),2540vs (BH), 1605w (br)(H,O) and 1094vs (br) cm-' (BF,-).NMR data in Table 1.Reaction of [2-(H,O)-2-(PPh3)-closo-2,l-PdTeB, OH9-(PPh,)][BF,] 2 with Carbon Monoxide.-Carbon monoxidewas bubbled through a solution of compound 1 (0.053 g,0.054 mmol) in toluene (30 cm3). There was an immediatecolour change from green to reddish pink. The flow of carbonmonoxide was stopped after 5 min and the volume of thesolution reduced to 6 cm3 and over-layered with light petroleum(b.p. 100-120 "C) (10 cm3). Red crystals of [2-(CO)-2-(PPh3)-closo-2,1-PdTeBloH9(PPh3)][BF4]~C6H5Me, 3*C6H,Me(0.023 g, 39.3%) were obtained (Found: C, 46.65; H, 4.50.C44H47B1 ,F,OP,PdTe requires C, 48.80; H, 4.40%). IR: v,,,2540vs (BH), 2518s (sh)(BH), 2118vs (CO) and 1078vs (br)cm-' (BF,-). "B-{'H} NMR (CH2C12, 294-298 K); 6 + 19.6(br, 1 B), + 11.0 (br, 1 B), + 10.4 [sh, 1 B, J("B-31P) ca.130 + 5 Hz], +5.9 (vbr, 2 B), - 1.5 (vsh, 1 B), - 10.1 (vbr, 1 B),- 12.2 (vbr, 1 B), - 15.0 (vbr, lB), - 18.6 (sh, 1 B) and -21.0(sh, 1 B).General Procedures for Reactions of Compound 2 withLigands L.-Procedure (a).One equivalent of L in CH,CI,(5 cm3) was added dropwise to a solution of compound 2 (ca.0.1 mmol) in CH,CI, (20 cm3). An immediate colour changeoccurred. The solution was stirred for 30 min, concentrated toca. 5 cm3 and layered with heptane (3 cm3).With Bu'NC. Recrystallisation from CH,Cl,-toluene (3 : 2)gave red-pink crystals of [2-(Bu'NC)-2-(PPh3)-closo-2,1-PdTe-B OH9( PPh 3)] [ BF,].C,H ,Me, 4*C6H ,Me (85.1%) (Found: C,49.20; H, 4.95; N, 1.55.C48H56B1 ,F,NP,PdTe requires C,50.65; H, 4.95; N, 1.25%). IR: vmaX 2558vs (BH), 2208vs (CN) and1058vs (br) cm-' (BF,-). NMR data in Table 1.With C,H NC. Recrystallisation from CH,CI,-heptane(3: 1) gave reddish pink crystals of [2-(C6H, 'NC)-2-(PPh3)-closo-2,1 -PdTeB oH9(PPh3)][BF4J~C6H,Me, 5-0.5CH2C1,(93.0%) (Found: C, 46.50; H, 5.00; N, 0.85. C43.5H51BllClF4-NP,PdTe requires C, 46.90; H, 4.60; N, 1.25%). IR: vmaX 2560vs(BH), 2520vs (BH), 2215vs (CN) and 1055vs (br) cm-' (BF,-)."B-{'H} NMR (CH,CI2, 294-298 K): 6 +18.7 (br, 1 B),ca. + 13.0 (br, 1 B), + 10.5 (br, 1 B), +9.7 [sh, 1 B, J("B-3'P)ca.132 f 5 Hz], cu. +8.0 (vbr, 1 B), - 1.3 (vsh, 1 B), ca. -6.0(vbr, 1 B), - 10.4 (vbr, 2 B), - 16.5 (sh, 1 B) and - 18.1 (sh, 1 B).With (R)-( + )-I-phenylethylarnine. Recrystallisation fromCH,CI,-heptane (3: 1) gave purple needles of [2-{ MeCH(Ph)-NH,)-2-(PPh3)-closo-2, 1 -PdTeB oHg(PPh3)][BF,] 7 (41.6%)(Found: C, 48.60; H, 4.65; N, 1.35. C,,H,oBl,F,NP2PdTerequires C, 48.90; H, 4.65; N, 1.30%). IR: v,,, 3314m (NH),3266m (NH), 2609m, 2524s, 2512vs (BH) and 1067s (br) cm-'(BF,-). "B-{ 'H} NMR (CH,CI,, 294-298 K): 6 + 17.4(br, 1 B),+9.3 [sh, 1 B, J("B-31P) ca. 132 & 5 Hz], +8.5 (br, 1 B),ca. +7.1 (vbr, 2 B), - 1.5 (vsh, 1 B), ca. -5.2 (vbr, 1 B),- 12.1 (vbr, 2 B), ca. - 19.9 (sh, 1 B) and -21.4 (sh, 1 B).With tetrahydrothiophene. Recrystallisation from CH,Cl,-heptane (3: 1) gave purple crystals of [2-(C,H,S)-2-(PPh3)-closo-2,1-PdTeBlOH,(PPh3)][BF, J 8 (87.1%) (Found: C, 45.10;H, 4.65; S, 3.05.C,oH,7BllF,P,PdSTe requires C, 45.90H, 4.55; S, 3.05%). IR: v, 2567 vs (BH) and 1062vs (br) cm-'(BF,-). NMR data in Table 1.Procedure (b). A large excess of L (5 cm3 of MeCN or thf, or11 equivalents of PMe,Ph) was added dropwise to a solution ofcompound 2 (0.1 mmol) in CH,Cl, (20 cm3). An immediatecolour change occurred. The solution was stirred for 30 min,concentrated to ca. 5 cm3 and layered with heptane (3 cm3).With excess of MeCN. Recrystallisation from CH,Cl,-heptane (3 : 1) gave purple crystals of [2-(MeCN)-2-(PPh3)-closo-2,1-PdTeB1 oHg(PPh3)][BF,] 6 (89.9%) (Found: C, 44.95;H, 4.45; N, 1.85.C,,H,,B,,F,NP,Pd~e requires C, 45.50H, 4.20; N, 1.40%). IR: vmaX 2558vs, 2548vs, 2511s (BH),2336w (CN), 2289w (CN) and 1054vs (br) cm-' (BF,-)."B-{'H} NMR (CH,Cl,, 294-298 K): 6 +18.1 (br, 1 B),+10.7 (br, 1 B), +9.9 [sh, 1 B, J(11B-31P) = 132 & 5 Hz], + 7.0 (br, 2 B), - 1.4 (vsh, 1 B), ca. -4.0 (vbr, 1 B), - 11.3 (vbr, 2B), - 18.3 (sh, 1 B) and - 19.7 (sh, 1 B).With excess of thf: Recrystallisation from thf-heptane(3: 2) gave blue crystals of [2-(C,H,0)-2-(PPh3)-cfoso-2,1-PdTeBloH9(PPh3)][BF,]~C,H80, 9.thf (92.9%) (Found: C,48.35; H, 5.25. C4,H5,B1 ,F,02P,PdTe requires C, 47.75; H,5.00%). IR: v,,, 2538vs (BH) and 1060vs (br) cm-' (BF,-). "B-{ 'Hf NMR (CH,Cl,, 294-298 K): 6+ 18.3 (br, 1 B), + 10.4 [sh,1 B, J("B-3'P) ca. 128 f 5 Hz], +9.7 (br, 1 B), +7.8 (br, 2 B),-1.5 (vsh, 1 B), ca.-1.6 (vbr, 1 B), -11.4 (vbr, 2 B), -19.9(sh, 1 B) and -21.1 (sh, 1 B)40 J. CHEM. SOC. DALTON TRANS. 1993Table 4 Details of the data collection and refinement for compounds 2.0.89CH2C1, and 3*C6H5Me"MoleculeCrystal size (mm)Crystal colour and shapeRange of orienting reflections (")Range of hkl collectedReflections collectedIndependent reflectionsObserved reflectionsMaximum and minimum transmission factorsLeast-squares parametersRR'b!?Maximum shiftleuorMaximum p/e A-32-0.89CH ,C10.23 x 0.26 x 0.40Green block7.5 < 0 < 17.510 01896285595 [ I > 3o(I)]0.98,0.955590.0380.0520.0012< 0.070.7h &17, k 0-19, I -25 to 253*c6 H Me0.36 x 0.33 x 0.15Dark red block7<0<1811 08810 5105439 [ I > 2.50(1)]0.86,0.725140.0540.07 10.001 25< 0.31.45h - 18 to 18, k (r13,1&39"Details in common: ~ 2 0 scans; scan width 0.7 + 0.35 tan@; 20 limits 4-54'.R' = (C[w(F0 - F c ) 2 ] / ~ ( w F 0 2 ) } f where w1 = 02(Fo) + gFo2.Table 5 Positional parameters and their estimated standard deviations for compound 2-0.89 CH2CI,X0.229 87(3)0.238 33(3)0.339 27(9)0.075 37(9)0.338 4(3)0.440 O(4)0.535 O(4)0.607 7(4)0.586 8 ( 5 )0.493 7(5)0.420 6(4)0.290 l(4)0.210 l(4)0.170 2(4)0.210 4(5)0.290 5(5)0.331 3(4)0.394 2(3)0.435 3(4)0.478 8 ( 5 )0.478 7(5)0.437 9(5)0.395 6(4)-0.043 8(4)-0.058 8 ( 5 )-0.150 8(6)-0.226 8 ( 5 )-0.21 1 9(4)- 0.122 2(4)0.098 2(4)0.028 O(4)v0.617 25(3)0.749 16(2)0.860 60(8)0.747 14(8)0.702 2(3)0.868 9(3)0.863 6(4)0.868 l(4)0.878 9(4)0.886 O(4)0.879 5(4)0.968 9(3)0.985 O(3)1.066 2(4)1.131 6(4)1.1 16 7(4)1.036 2(4)0.840 5(3)0.761 8(3)0.742 9(4)0.803 6(5)0.882 O(4)0.901 O(4)0.781 O(3)0.849 l(4)0.869 8 ( 5 )0.823 9(5)0.756 7(5)0.736 O(4)0.652 6(3)0.6 16 9(4)0.997 59(2)0.9 12 64(2)0.953 46(6)0.765 93(6)0.842 5(2)0.902 9(3)0.928 O(3)0.887 l(4)0.820 2(4)0.793 9(3)0.834 9(3)0.954 4(2)0.988 4(2)0.987 8(3)0.953 3(3)0.920 8(3)0.921 5(3)1.036 7(2)1.050 4(3)1.161 9(3)1.149 4(3)1.086 6(3)0.737 O(3)0.692 2(3)0.668 8(4)0.687 O(4)0.730 8(3)0.755 7(3)0.718 2(2)0.673 7(3)1.112 5(3)The site occupancy is 1.0 unless otherwise specified.Y0.045 O(5)0.129 8(6)0.201 O(5)0.185 8(4)0.154 3(4)0.220 5(4)0.276 7(5)0.264 8(6)0.198 l(6)0.144 3(5)0.151 5(4)0.078 3(5)0.084 4(6)0.162 l(5)0.090 l(4)0.026 1 ( 5 )0.038 4(5)0.096 8(4)0.4 19 8(4)0.520 O(5)0.388 5(6)0.494 7( 10)0.365 4( 1 1)0.456 4( 13)0.411 l(25)0.267 6(3)0.313 3(6)0.420 6( 5 )0.356 O( 12)-0.012 7(5)-0.007 6(4)Y0.539 7(4)0.498 7(4)0.534 8(5)0.61 1 4(4)0.831 7(3)0.822 O(4)0.890 4( 5 )0.968 O(5)0.980 6(4)0.91 1 6(4)0.626 9(4)0.582 O(4)0.663 O(5)0.757 9(4)0.724 2(3)0.634 6(4)0.657 5(5)0.759 2(4)0.803 2(4)0.740 6(4)0.566 2(4)0.467 33)0.483 9(8)0.571 6(8)0.434 O( 1 1)0.515 9(12)0.493 8(26)0.337 5(4)0.357 6(6)0.347 O(4)0.373 2(9)Site occupancy0.643 O(3)0.655 8(3)0.697 2(3)0.728 4(3)0.743 7(2)0.697 3(3)0.681 6(3)0.709 3(4)0.755 7(4)0.772 8(3)0.888 8(3)0.956 9(4)1.025 8(3)0.860 8(3)0.885 9(3)0.966 9(3)0.991 l(3)0.923 8(3)0.908 5(3)0.914 5(4)0.887 3(4)0.830 O(4)0.815 8(6) 0.60.928 7(9) 0.40.861 2( 10) 0.60.902 8( 17) 0.41.098 l(3) 0.890.980 3(3) 0.531.162 8(3) 0.361.068 O(9) 0.891.002 7(3)With e.xcess of PMe,Ph.Recrystallisation from CH,Cl,-heptane (3 : 2) gave red crystals of [2,2-(PMe2Ph),-closo-2,1-PdTeB,,H,(PPh3)][BF4]~0.5CH2C12, 10~O.5CH2C1, (75.0%)(Found: C, 40.90; H, 4.75. C,,.,H,,B, ,ClF,P,PdTe requires C,40.65; H, 4.70%).TR: vmaX 2509m, 2557vs, 2552~s~ 2537~s~ 2523vs(BH) and 1063vs cm-' (BF,-). NMR data in Table 1.Structure Determination of Compounds 2=0.89CH2C1, and3*C,H,Me.-Crystal data for 2. C36H41B1 ,F,OP,PdTe-0.89CH2C1,, M = 1056.2, monoclinic, space group P2,/c7(I = 14.073(3), b = 15.640(2), c = 20.262(6) A, p = 94.80(2)",D, = 1.58 g ~ m - ~ , U = 4444(2) A3, Z = 4, 28,,, = 54", ~ ( M o -Kcc) = 12.8 cm-', h(M0-Ka) = 0.701 73 A, F(OO0) = 2085,T = 288 K, final R = 0.038, R' = 0.052 (statistical weights,559 parameters) for 5595 observed reflections.Crystal data for 3. C3,H3,Bl,F40P,PdTe~C,H,, M =1082.7, monoclinic, space group P2,/c, a = 14.509(3), b =10.732(1), c = 31.377(8) A, p = 97.49(2)", D, = 1.49 g ~ m - ~ ,U = 4844(2) A3, 2 = 4, 28,,, = 54", p(Mo-Ka) = 10.8 cm-',h(M0-Ka) = 0.701 73 A, F(Oo0) = 2152, T = 293 K, finalR = 0.054, R' = 0.071 (statistical weights, 542 parameters)for 5439 observed reflections.Both compounds were analysed in a similar way (detailsof data collection and structure determination are summarisedin Table 4).Accurate cell dimensions and the crystal orient-ation matrix were determined by a least-squares refinementof the setting angles of 25 reflections. Data were collectedon a CAD-4 diffractometer using graphite-monochromated(Mo-Ka) radiation. The intensities of three reflections measuredat 120 min intervals showed no loss in intensity. Lorentz,polarisation and absorption corrections were applied to thedata. Both structures were solved using the Patterson heavy-atom method which revealed the positions of the Te and Pdatoms.The remaining non-hydrogen atoms were located iJ. CHEM. SOC. DALTON TRANS. 1993 41Table 6 Positional parameters and their estimated standard deviations for compound 3CH,H,MeY0.060 59(4)0.121 80(4)0.362 32( 14)0.033 14( 14)0.163 9(6)0.1 76 4( 5)0.042 l(4)0.159 9(6)0.052 l(7)0.076 l(7)0.331 3(5)0.278 l(6)0.239 3(7)0.234 0(8)0.268 8(8)0.308 O(6)0.467 4(6)0.497 4(7)0.578 2(7)0.628 S(7)0.600 O( 7)0.520 3(6)0.400 O(6)0.492 6(6)0.519 2(7)0.453 4(9)0.362 3(8)0.334 7(6)- 0.090 3( 5)-0.131 6(6)-0.226 6(6)-0.279 5(6)Y0.454 4 1 (5)0.219 92(5)0.178 32(20)0.054 55( 19)0.960 O(7)0.815 l(6)0.914 6(6)1.014 8(7)0.164 3(10)0.186 l(10)0.126 0(8)0.214 l(10)0.178 8(11)0.055 O( 14)O.OO0 6(9)0.260 3(8)0.260 l(9)0.324 4( 11)0.385 4( 10)0.386 3(10)0.324 l(10)0.039 9(8)0.007 5( 1 1)- 0.032 9( 1 1)-0.100 2(12)-0.179 4(11)- 0.147 8(9)-0.039 7(8)0.092 3(7)0.169 6( 8)0.I92 5(9)0.136 5( 10)Z0.371 77(2)0.386 78(2)0.433 38(7)0.352 44(7)0.097 l(3)0.047 2(2)0.051 O(2)0.028 2(3)0.471 4(4)0.443 2(3)0.479 8(3)0.506 2(3)0.542 9( 3)0.552 4(4)0.528 O(4)0.490 8(3)0.455 3(3)0.498 9(3)0.514 9(4)0.486 9(4)0.443 7(4)0.427 6(3)0.407 l(3)0.410 6(4)0.392 S(4)0.371 l(4)0.366 9(4)0.384 5(3)0.337 O(3)0.363 7(3)0.356 5(3)0.322 2(4)X-0.236 8(6)-0.143 3(6)0.028 7(6)0.096 9(6)0.094 4(8)0.023 l(8)-0.044 8(7)-0.042 l(6)0.072 1(6)0.122 7(6)0.159 9(8)0.148 5(8)0.099 O(7)0.059 9(6)0.358 3( 13)0.384 8(20)0.444 5(21)0.477 6( 16)0.451 l(20)0.391 5(19)0.294 2( 16)0.136 O(9)0.1 17 3(7)0.157 6(8)0.205 6(8)0.201 3(6)0.225 5(6)0.224 5(7)0.277 9(8)0.304 O(6)0.275 4(6)0.319 4(6)Y0.060 6( 10)0.039 0(8)-0.078 9(7)-0.098 8(9)-0.202 O(9)-0.284 2(9)-0.269 l(8)-0.168 4(8)-0.011 5(8)-0.122 9(8)-0.167 8(10)-0.103 5(12)0.006 l(11)0.051 4(8)1.119 8(19)1.158 O(28)1.084 O(38)0.971 8(34)0.933 6(25)1.007 6(2 1)1.199 4(23)0.927 2( 10)0.320 5(9)0.490 2(9)0.535 6(9)0.393 6(8)0.228 l(8)0.359 8(9)0.490 4(9)0.436 l(8)0.276 l(8)0.337 6(9)z0.295 O( 3)0.302 5(3)0.387 8(3)0.422 3(3)0.448 7(3)0.441 5(3)0.407 2(4)0.380 7(3)0.305 2(3)0.307 3(3)0.272 3(4)0.233 9(4)0.230 4( 3)0.265 8(3)0.199 2(6)0.241 5(7)0.269 4(8)0.254 9( 11)0.212 6(12)0.184 7(9)0.169 3(8)0.055 l(4)0.322 5(3)0.321 3(4)0.377 6(4)0.41 5 O(3)0.341 8(3)0.306 7(3)0.338 2(4)0.392 6(3)0.394 7(3)0.348 6(3)subsequent Fourier synthesis.Hydrogen atoms (visible indifference maps) were included in the refinement at geo-metrically idealised positions, but restrained to ride on thecarbon or boron atom to which they were bonded (C-H 0.95 orB-H 1.08 A). The hydrogen atoms on the water molecule incompound 2 were also located from difference maps andincluded in the structure-factor calculation at these positions;no other peaks > 0.3 e A-3 were present near this oxygen atom.Refinement was by full-matrix least squares calculations on F,initially with isotropic and later with anisotropic thermalparameters for non-H atoms.In molecule 2 it became obviousduring refinement that there was disorder associated with the[BF,] - anion which was also involved in hydrogen bonding tothe CH2CI, solvate present in the lattice. There were fivefluorine sites, which refined with variable site occupancy tovalues of 1.0, 1.0, 1.0, 0.6 and 0.4. The boron atoms weredisordered over two sites with occupancies of 0.6 and 0.4. TheCH,CI, molecule was disordered over two sites which refinedanisotropically to values of 0.53 and 0.36. The disorder was suchthat the disordered [BF,] - anion and CH,CI, were associatedtogether through hydrogen bonding about an inversion centre.In 3 a difference map calculated at the beginning of the refine-ment showed that there was a toluene molecule of solvationpresent in the asymmetric unit.By careful selection of the maxi-ma from a rather diffused electron-density area the positionsof the carbon atoms in the toluene molecule were determined.Scattering factors and anomalous dispersion corrections weretaken from ref. 15. All calculations were performed on a SiliconGraphics 4D-380 computer using the NRCVAX programs.16Atomic coordinates are given in Tables 5 and 6 for compounds2 and 3 respectively. Figs. 1 and 3 were prepared usingORTEP I1 in conjunction with the NRCVAX suite ofprograms.Additional material available from the Cambridge Crystallo-graphic Data Centre comprises H-atom coordinates, thermalparameters and remaining bond lengths and angles.AcknowledgementsA generous loan of palladium salts from Johnson Matthey plc isgratefully acknowledged by T.R. S. G. F. would like to thankthe Natural Sciences and Engineering Research Council(Canada) for Grants in Aid of Research.References1 Part 11, G. Ferguson, J. F. Gallagher, M. McGrath, J. P. Sheehan, T.R. Spalding and J. D. Kennedy, preceding paper.2 J. D. Kennedy, Prog. Inorg. Chem., 1984, 32, 519; 1986, 34, 211;Baron Hydride Chemistry, ed. E. L. Muetterties, Academic Press,New York, 1975; R. N. Grimes, in Comprehensive OrganometallicChemistry, ed. G. Wilkinson, Pergamon, Oxford, 1982, voi. 1, 459;L. J. Todd, in Comprehensiue Organometallic Chemistry, ed.G. Wilkinson, Pergamon, Oxford, 1982, vol. 1,543.3 S. G. Shore, J. D. Ragaini, T. Schmitkons, L. Barton, G. Medfordand L. Plotkin, Abstracts 4th Inter. Meeting Boron Chem.,IMEBORON IV, 1979, Abstract 07.4 C. J. Jones, J. N. Francis and M. F. Hawthorne, J. Am. Chem. SOC.,1973,95,7633.5 M. F. Hawthorne, L. F. Warren, K. P. Callahan and N. F. Travers,J. Am. Chem. SOC., 1971,93,2407.6 H. C. Kang, S. S. Lee, C. B. Knobler and M. F. Hawthorne, Inorg.Chem., 199 1,30,2024.7 A. J. Deeming, I. P. Rothwell, M. B. Hursthouse and L. New,J. Chem. Soc., Dalton Trans., 1978, 1490.8 P. Castan, J. Jaud, S. Wimmer and F. L. Wimmer, J. Chem. SOC.,Dalton Trans., 1991, 1155.9 M. Grassi, S. V. Meille, A. Musco, R. Pontellini and A. Sironi,J. Chem. Soc., Dalton Trans., 1989, 61 5.10 B. P. Andreini, D. B. Dell’Amico, F. Calderazzo and G. Pelizzi,J. Organornet. Chem., 1988,354, 369.I 1 G. Ferguson, M. Parvez, J. A. MacCurtain, 0. Ni Dhubhghaill,T. R. Spalding, X. L. R. Fontaine and J. D. Kennedy, J . Chem. SOC.,Dalton Trans., 1987,699.12 Faridoon, 0. Ni Dhubhghaill, T. R. Spalding, G. Ferguson,B. Kaitner, X. L. R. Fontaine and J. D. Kennedy, J. Chem. Soc.,Dalron Trans., 1989, 165742 J. CHEM. SOC. DALTON TRANS. 199313 G. Ferguson, J. D. Kennedy, X. L. R. Fontaine, Faridoon and 16 E. J. Gabe, Y. LePage, J.-P. Charland, F. L. Lee and P. S. White,14 P. Castan, F. Dahan, S. Wimmer and F. L. Wimmer, J. Chem. Soc., 17 C. K. Johnson, ORTEP 11, Report ORNL-5138, Oak Ridge15 International Tables .for X-Ray Crystallography, Kynoch Press,T. R. Spalding, J. Cllem. SOC., Dalton Trans., 1988,2555.Dalton Trans., 1990, 2679.Birmingham, 1974, vol. 4.J. Appl. Crystullogr., 1989,22, 384.National Laboratory, Oak Ridge, TN, 1976.Received 7th July 1992; Paper 2/03570

ISSN:1477-9226    

DOI:10.1039/DT9930000035

出版商:RSC    

年代:1993

数据来源: RSC