|
1. |
Iridium thioether chemistry: the synthesis and structures of [IrL2][PF6]3and [IrHL2][PF6]2(L = 1,4,7-trithiacyclononane) |
|
Dalton Transactions,
Volume 1,
Issue 6,
1990,
Page 1759-1764
Alexander J. Blake,
Preview
|
PDF (802KB)
|
|
摘要:
J. CHEM. SOC. DALTON TRANS. 1990 Iridium Thioether Chemistry The Synthesis and Structures of [IrL,] [PF,] and [IrHL,J[PF,] (L = 1,4,7-trithiacyclononane) t Alexander J. Blake Robert 0. Gould Alan J. Holder Timothy 1. Hyde Gillian Reid and Martin Schroder Department of Chemistry University of Edinburgh West Mains Road Edinburgh EH9 3JJ Reaction of [{IrCl(C8Hq4),}J with 4 molar equivalents of 1,4,7-trithiacycIononane (L) in water- methanol (2:1 v/v) in the presence of HBF affords the iridium(i1i) hydrido complex [IrHLJ2+. The complex [IrHL,] [PF,],*2MeN02 crystallises in the monoclinic space group Cc a = 19.456 0(17) b = 8.1 52 5(9) c = 21.935(3) A p = 11 7.008(7)" and Z = 4. The single-crystal X-ray structure of the complex shows one L ligand bound facially to lrlrr Ir-S(l) (trans to H) 2.476(5) lr-S(4) 2.298(5) lr-S(7) 2.321 (5) A with the second L bound as a bidentate ligand through only two S donors Ir-S(11) 2.344(5) lr-S(41) 2.31 9(5) A; the dangling donor S(71) lies 4.329(6) A from the iridium centre.The sixth co-ordination site is taken up by a hydride Ir-H 1.58(6) A. Treatment of [IrHL,] [PF,] with aqueous HNO affords the homoleptic thioether complex [ITL,]~'. The complex [IrL,] [PF,],*5MeN02 crystallises in the monoclinic space group C2/c a = 8.581 7(13) b = 21.338(4) c = 23.482(7) A p = 90.94(2)" and Z = 4. The single-crystal X-ray structure of the complex confirms homoleptic hexathia co-ordination at a centrosymmetric octahedral iridium( 111) centre Ir-S(l) 2.342(3) lr-S(4) 2.341 (3) lr-S(7) 2.338(3) A. The redox properties of [IrL2l3+ are discussed and compared to those of the rhodium( 111) analogue [ R hL,I3+.Spectroelectrochemical measurements using a u.v.-visible optically transparent electrode system confirm the isosbestic and reversible interconversion of [RhL,I3+ [RhL,I2+ and [RhL,] +. Our studies on platinum-group metal complexes of 1,4,7-tri- thiacyclononane (L) have led to the isolation and characteris- ation of a range of unusual homoleptic thioether complexes of the type [ML,]"+ (M = Ru Os Rh Pd or Pt; x = 2 or 3).14 However the synthesis of [IrL,] + has presented particular difficulties due to the high kinetic inertness of the d6 iridium(rI1) centre. Attempts to synthesise [IrL2I3+ from a range of iridium(II1) starting materials have led to the isolation of the desired complex in extremely low and unworkable yields.We argued that an alternative route might be developed involving addition of 2 equivalents of L to d8 Ir' to afford [IrL,]'. This highly reactive species prepared perhaps only in situ could then be oxidised up to the desired d6 iridium(rI1) complex [IrL,] + . The redox interconversion of d6 d7 and d8 metal complexes with L and its N-donor analogue 1,4,7-triazacyclononane has been shown previously for complexes of Pt,295*6 Pd,7*8 and Rh,799 suggesting that the analogous iridium(m) -(II) -(I) chemistry would be a viable target. We report herein the high-yield synthesis and structure of the [IrL213+ cation prepared from [{1rc1(C8Hl4),},]. The syn- thesis and structure of an unusual iridium(II1) hydrido complex [IrHL212+ is also described.Results and Discussion Reaction of [{IrC1(c8Hl4),},] with 4 molar equivalents of L in water-methanol (2 1 v/v) under reflux for 16 h under N in the presence of 40% HBF affords a colourless solution from which the complex cation [IrHL,]" can be isolated as a PF6- salt in 70% yield. The 'H n.m.r. spectrum in CD3CN shows a resonance at 6 -13.40 assigned to the metal hydride. In addition multiplet resonances are observed in the range 6 2.6- 4.2 (Figure 1) suggesting asymmetric binding of L to the metal centre. This is confirmed by the 13C n.m.r. spectrum which shows six resonances for the methylene C centres of co- ordinated L at 31.35 35.61,35.88,39.01,39.09 and 40.60 p.p.m.L Fast-atom bombardment mass spectroscopy of [IrHL,][PF,] shows peaks at m/z 699 and 553 assigned to the fragments ['931rHL2(PF6)] + and [1931rL,] + respectively. The i.r. spec- trum of [IrHL,][PF,] shows in addition to bands for co- ordinated L and PF6- counter ion an Ir-H stretching vibration at 2 180 cm-' while elemental analysis confirms the stoicheio- metry of the product. Colourless crystals of [IrHL,][PF6],-2MeN0 were grown by vapour diffusion of diethyl ether into a solution of the complex in MeNO,. The single-crystal X-ray structure of the complex confirms (Figure 2) Ir"' bound to two L ligands and a hydride ligand. One L is bound facially to Ir"' as a tridentate ligand Ir-S(l) (trans to H) 2.476(5) Ir-S(4) 2.298(5) Ir-S(7) 2.321(5) A S(l)IrS(4) 87.28(17) S(l)IrS(7) 87.70(17) S(4)IrS(7) 89.81(18)" with elongation of the Ir-S(l) bond reflecting the high trans influence of hydride ligands.The second L is bound only as a bidentate ligand through two S donors Ir-S(11) 2.344(5) Ir-S(41) 2.319(5) A S(ll)IrS(41) 86.75(18)". The third S donor is non-bonding with S(71) lying 4.329(6) A from the iridium(II1) centre; the Ir-H distance is 1.58(6) A. Relatively few macrocyclic iridium(rI1) hydride complexes have been The complex [Ir(oep)H] (H,oep = 2,3,7,8,- 1759 12,13,17,18-octaethylporphyrin) is a very useful precursor for the synthesis of the metal-metal bonded dimer [{Ir(oep)},] which activates C-H bonds and 02." The binding of L as a t Supplementary data available see Instructions for Authors J.Chem. SOC. Dalton Trans. 1990 Issue 1 pp. xix-xxii. HOD 1 1760 5 13 -1 4 4 2 A - 6 Figure 1. Proton n.m.r. spectrum (80 MHz CD,CN 298 K) of [IrHL,] + Figure 2. Single-crystal X-ray structure of [IrHL2I2+ with numbering scheme adopted n 3 P J. CHEM. SOC. DALTON TRANS. 1990 bidentate ligand to Ir"' is particularly interesting. The ligand is pre-organised '' for facial bonding to transition-metal centres with the three S donors in the metal-free ligand lying in endo position^.'^ Thus it forms a wide range of very stable octahedral transition-metal complexes in which the minicycle binds facially and acts as a formal six-electron donor to the metal ion.' This is similar to the facial binding of arene and pyrazolylborate ligands to metal centres.However if the electronic properties of the metal centre disfavour facial binding or d" gold(1) '' species bidentate monodentate or inter- of L such as for d8 palladiurn(~r),~*'~ platinum(~r),' gold(111),' mediate co-ordination of L is observed. In the complex [IrHLJZ+ however facial binding of L is not disfavoured by the d6 iridium(II1) centre but by the presence of the strongly co- ordinating H - ligand. The complex [IrHL,12 + shows an irreversible reduction by cyclic voltammetry at Ep = - 1.95 V us. ferrocene-ferrocenium at -40 "C. Treatment of [IrHL2]2+ with aqueous HNOJ under reflux affords [IrLJ3 + in 75% yield thus transforming the bidentate four-electron donor L to a tridentate six-electron donor.The H n.m.r. spectrum of [IrLJ3+ in CD,CN shows a symmetric multiplet centred at 6 3.23 as observed for the related complexes [ML,I3+ (M = C O ' ~ or Rh'). No hydrido resonances are observed in the 'H n.m.r. spectrum of the product. The 13C n.m.r. spectrum shows a single resonance at 6 36.60 p.p.m. Fast-atom bombardment mass spectroscopy of [IrL,][PF,] shows peaks at m/z 843 697 and 551 assigned to ['931rLz(PF6)2]+ ['931rLz(PF6) - HI+ and ['931rL - 2H]+ respectively. The mass spectroscopic fragmentation pattern suggests that deprotonation of the co-ordinated L ligands occurs during the ionization process. Interestingly we have recently found that the complexes [MLJ3+ (M = Co Rh or Ir) and related thioether complexes incorporating highly charged metal centres can be deprotonated in solution; this is followed by a ring-opening reaction to afford vinyl thioether complexes.' The above together with elemental analysis and i.r. and electronic spectroscopic data is consistent with symmetric binding of two L ligands to Ir"' in [ITL,][PF~]~. Single crystals of [IrL2][PF6],-5MeNo were grown by vapour diffusion of diethyl ether into a solution of the complex in MeNO,. The single-crystal X-ray structure of the complex (Figure 3) confirms homoleptic hexathia co-ordination to Ir"' in the centrosymmetric cation Ir-S( 1) 2.342(3) Ir-S(4) 2.341(3) Ir-S(7) 2.338(3) A S(l)IrS(4) 88.28(10) S(l)IrS(7) 89.1 1(10) S(4)IrS(7) 88.46( 10)". The narrow range of Ir-S bond lengths in this compound is as expected for bis(sandwich) complexes of L with d6 metal centres,'~~ with the related d6 rhodium(II1) complex [RhLJ3 + showing Rh-S( 1) 2.33 1 6( 14) Rh-S(4) 2.333 5(12) Rh-S(7) 2.333 5(12) A S(l)RhS(4) 88.78(5) S( 1)RhS(7) 88.78(5) S(4)RhS(7) 88.84(4)".' The complex cation [RhLJ3 + shows two one-electron reductions by cyclic voltammetry in MeCN at E+ = -0.71 and - 1.08 V us.ferrocene-ferrocenium. These reductions have been assigned to Rh"'-Rh" and Rh"-Rh' couples respectively Electrogeneration of the mononuclear d rhodium(I1) complex [RhL,]' + has been achieved and the metal-radical species identified by e.s.r. spectros~opy.~ Clearly it was important to determine whether the iridium(Ir1) analogue [IrL,] + showed similar redox behaviour. Cyclic voltammetry of [IrLJ3+ in MeCN (0.1 mol dm-3 NBun,PF6) at platinum electrodes shows a reduction at Epc = - 1.38 V us.ferrocene-ferrocenium. This reduction is essentially irreversible down to -40 "C. This contrasts with the two reduction processes for [RhL,I3 + which are reversible under the same conditions. Coulometric measurements obtained by controlled-potential electrolysis at - 1.6 V confirm the reduction of [IrLJ3+ to be a one-electron process. J. CHEM. SOC. DALTON TRANS. 1990 E,,,. 300 700 600 4 00 500 hlnm 1761 irreversibility of the reduction wave by cyclic voltammetry. The reduction of [IrL,] + was monitored spectroelectrochemically using an optically transparent electrode system. Figure 4 shows the changes in the electronic spectrum on reduction of [IrL,I3+ in MeCN at - 1.55 V at -22 "C.Importantly the reduction occurs isosbestically with loss in intensity and a shift to higher energy of the S+Ir charge-transfer band from h,,,. = 229 nm = 25 OOO dm3 mol-' cm-' for the iridium(n1) starting material to h,,,. = 225 nm = 16 800 dm3 mol-' cm-' for the reduction product hiso = 248 and 222 nm. Consistent with the voltammetric and coulometric measurements reoxidation of the reduction product to the iridium(Ir1) species does not occur up to 0.0 V. No significant paramagnetic signal has thus far been detected by e.s.r. spectroscopy for the reduction product. These results contrast with spectroelectrochemical measure- ments on the reduction of [RhL,13+ under the same conditions.Figure 5 shows the changes in the electronic spectrum of [RhLJ3+ on reduction to [RhL2I2+ at -0.88 V and to [RhL,] + at - 1.30 V vs. ferrocene-ferrocenium. Reduction of [RhL2I3+ (Amax. = 268 nm = 30 600 dm3 mol-' cm-') to Figure 4. Reduction of [IrL,I3 + by controlled-potential electrolysis at - 1.55 V us. ferrocene-ferrocenium in MeCN (0.1 mol dm-3 NBu",PF,) 200 at -22 OC c b I [RhL,]'+ (Amax. = 307 and 257 nm emax. = 6 200 and 20 100 dm3 mol-' cm-') occurs isosbestically hiso = 340,305,258 and 208 nm. As for the iridium system reduction leads to a loss in intensity and shift to higher energy of the S+M charge-transfer band at 268 nm consistent with increased electron density at the metal centres. Conversion of [RhL2I2+ to [RhL2]+ (Amax.= 361 and 254 nm E,,,. = 2 800 and 13 500 dm3 mol-' cm-') also occurs essentially isosbestically hi = 332 and 246 nm although the high reactivity of the rhodium(1) species in solution does lead to some decomposition. Cycling between [RhL,] + [RhL,] + and [RhL,I3+ occurs reversibly and isosbestically confirming the ready chemical interconversion of the rhodium- (111) -(II) and -(I) comple~es.~ The porphyrin ' ' and organometallic ' * chemistry of d7 iridium(i1) species is dominated by binuclear metal-metal bonded species. The cyclic voltammetric coulometric and spectroscopic data obtained thus far on the reduction of [IrL2I3+ are consistent with the formation of such a binuclear iridium@) species although this tentative assignment clearly requires further confirmation.Current work is aimed at characterising the redox product(s) of [IrL,I3 + and monitoring the role of metal-metal bonded species in the reduction of related complexes of Rh"' and Ir"' with polythia and polyaza macrocyclic ligands. Experimental Infrared spectra were measured as KBr and CsI discs using a Perkin-Elmer 598 spectrometer over the range 200-4 O00 cm-'. Electrochemical measurements were performed on a Bruker E3 10 Universal Modular Polarograph. All readings were taken using a three-electrode potentiostatic system in acetonitrile con- taining 0.1 mol dm-3 NBun4PF6 or NBun4BF4 as support- ing electrolyte. Cyclic voltammetric measurements were carried out using a double platinum electrode and a Ag-AgC1 refer- ence electrode.All potentials are quoted uersus ferrocene-ferro- cenium. U.v.-visible spectra were measured in quartz cells using a Perkin-Elmer Lambda 9 spectrophotometer. Spectroelectro- chemical measurements were carried out in a quartz cell (path length 0.5 mm) fitted with a fine platinum-rhodium gauze as a working electrode. The platinum auxiliary electrode and Ag-Ag + reference electrode were fitted into a quartz extension attached to the cell and were protected from the bulk solution by porous glass frits. The temperature of the cell was maintained and controlled by the passage of dry pre-cooled nitrogen gas around the assembly and monitored using a thermocouple and digital thermometer. Microanalyses were performed by the Edinburgh University Chemistry Department microanalytical XI nm Figure 5.(a) Reduction of [RhL213+ to [RhL2]'+ by controlled- potential electrolysis at - 0.88 V us. ferrocene-ferrocenium in MeCN (0.1 mol dm-3 NBu",PF,) at -22 "C. (b) Reduction of [RhLJ'' to [RhL,] + by controlled-potential electrolysis at - 1.30 V us. ferrocene- ferrocenium in MeCN (0.1 mol dm - NBu",PF,) at - 22 "C However the reduction product cannot be reoxidised to [IrL2I3+ on changing the potential to 0.0 V consistent with the of 1762 service. E.s.r. spectra were recorded as solids or as frozen glasses down to 77 K using a Bruker ER200D X-band spectrometer. Mass spectra were run by electron impact on a Kratos MS902 and by fast-atom bombardment on a Kratos MS 50TC spectro- meter.Synthesis [IrHL,][PF,],.-Reaction of [{1rC1(C8H1,),},] (0.16 g 0.17 mmol) with L (0.135 g 0.75 mmol) in refluxing water-methanol (2:1 v/v) (30 cm3) containing 40% HBF (0.5 cm3) for 16 h under N affords a colourless solution. The MeOH was removed in uacuo and the aqueous solution extracted with CH2C1 to remove unreacted L and cyclo-octene. The aqueous solution was reduced to 10 cm3. Addition of an excess of NH4PF and cooling of the solution afforded a near white product which was recrystallised from MeNO,-diethyl ether to give [IrHL,][PF& as a colourless product in 70% yield (Found C 17.2; H 3.00. Calc. for [IrHL2][PF6], C 17.1; H 3.00%). Infrared spectrum 2 180 cm-' [v(Ir-H)] in addition to bands assigned to L and PF; counter ion. N.m.r.(CD,CN 298 K) 'H (80 MHz) 6 - 13.40 (s Ir-H) and 4.2-2.6 (m CH,); I3C (50.32 MHz) 6 31.35 35.61 35.88 39.01 39.09 and 40.60 p.p.m. (CH,). Fast-atom bombardment mass spectrum (3-nitrobenzyl alcohol) m/z 699 and 553; calc. for ['931rHL2(PF6)]+ and [1931rL2]+ 699 and 553 respectively. X-Ray Structure Determination of [IrHL2][PF,],*2MeN0,-. -A colourless columnar crystal (0.2 x 0.25 x 0.6 mm) suitable for X-ray analysis was obtained by vapour diffusion of diethyl ether into a solution of the complex in MeNO,. Crystal data. C 2H2,F121rP,S,~2MeN02 A4 = 965.8 monoclinic space group Cc (no. 9) a = 19.456 0(17) b = 8.152 5(9) c = 21.935(3) A p = 117.008(7)" U = 3 099.8 A3 [from 28 values of 26 reflections measured at +o (28 = 29- 30° h = 0.71073 A)] 2 = 4 D = 2.069 g ern-, T = 295 K p = 4.878 mm-' F(OO0) = 1 888.Data collection and processing. Stoe STADI-4 four-circle diffractometer graphite-monochromated Mo-K X-radiation T = 295 K 0-28 scans with o scan width (1.05 + 0.347 tane)o 2 250 data measured (28,,,. 45O h -20 to 20 k 0-8 1 0-23) 1 999 unique (Rint = 0.029) initial absorption correction by means of y scans giving 1 859 with F 2 60(F) for use in all calculations. Slight isotropic crystal decay (ca. 11%) corrected for during data reduction. Structure solution and reJnement. The Ir was found from a Patterson synthesis and iterative cycles of least-squares refinement and difference Fourier synthesis located all non-H atoms. Attempts to solve and refine the structure in the corresponding centric space group (C2/c no.15) were unsuccessful. At isotropic convergence final correction for absorption was made using DIFABS.I9 Disorder in one PF anion was modelled by allowing partial occupation of alternative sites by some F atoms. The Ir S P and fully occupied F atoms were then refined (by least squares on F),' with anisotropic thermal parameters with macrocyclic H atoms included at fixed calculated positions solvent H atoms as part of rigid groups and the Ir-bound H refining freely. At final convergence R R' = 0.0352,0.0422 respectively S = 1.077 for above 0.73 e A-3 the weighting scheme w' = 02(F) + 274 refined parameters. The final A F synthesis showed no peak O.OO0 258F' gave satisfactory agreement analyses and in the final cycle (A/O),,,,~.was 0.31. Although the alternative polarity for the structure gave almost identical residuals and errors on refined parameters the derived molecular geometry was significantly different however a published procedure based on those reflections calculated to be most sensitive favoured one polarity and all results refer to this. Table 1 gives bond lengths I .58(6) 2.476( 5) 2.298(5) 2.32 l(5) 2.344(5) 2.3 19(5) 1.85 5( 19) 1.869(21) 1.47( 3) 1.844( 19) 1.8 5 l(20) 1.56(3) Ir-H( 1 ) Ir-S( 1) Ir-S(4) Ir-S(7) Ir-S( 1 1) Ir-S(4 1 ) S( 1 )-C(2) S( 1 bC(9) C(2)-C(3) C(3)-S(4) S(4)-C(5) C(5tC(6) H( 1)-Ir-S( 1) H( l)-Ir-S(4) H( 1 )-Ir-S( 7) H(1)-Ir-S(11) H ( 1 )-I r-S(4 1 ) S( l)-Ir-S(4) S( 1)-Ir-S(7) S(1)-Ir-S(l1) S( l)-Ir-S(41) S(4)-Ir-S( 7) S(4)-Ir-S( 11) S(4)-I r-S(4 1 ) S(7)-Ir-S( 11) S(7)-Ir-S(41) S(l l)-Ir-S(41) Ir-S( 1)-C(2) Ir-S( 1)-C(9) C(2tS(l)-C(9) S(ltC(2)-C(3) C(a-C(3)-S(4) Ir-S(4)-C( 3) Ir-S(4)-C( 5 ) J.CHEM. SOC. DALTON TRANS. 1990 Table 1. Bond lengths (A) angles and torsion angles (") with estimated standard deviations (e.s.d.s) for [IrHL2][PF,],-2MeN02 173.1(23) 96.5(23) 98.1(23) 84.0(23) 84.6(23) 87.28( 17) 87.70( 17) 92.14(17) 89.46( 17) 89.81( 18) 178.67( 18) 92.06( 18) 9 1.35( 1 8) 176.52(18) 86.75( 18) 102.2(6) 100.9(7) 102.3(9) 111.1(13) 1 15.2( 13) 102.2(6) 105.3(6) C(9)-SU>-C(2)-C(3) C(2)-S(1)-C(9)-C(8) S( l)-C(2)-C(3)-S(4) C(2)-C(3)-S(4)-C(5) C(3)-S(4)-C(5kC(6) S(4kC(5kC(6)-S(7) C(5)-C(6)-S(7)-C(8) C(W(7)-C(8)-C(9) S(7>-C(8)-C(9)-S(1) C(91)-S(ll)-C(21)-C(31) C(2 1 )-S( 1 1)-C(9 1)-C(8 1) S( 1 1)-C(21)-C( 3 1)-s(41) c(21)-c(3 1)-s(41)-c(5 1) C(3 1 )-S(41)-C( 5 1 kC(6 1) 92.6( 18) S(4 1)-C(5 1)-C(6 1 )-S(7 1) - 74.4(20) C(5 l)-C(61)-S(7 1)-C(8 1) 109.0(16) C(61)-S(7 1)-C(8 1)-C(9 1) - 107.2(16) S(71)-C(8l)-C(9l)-S(ll) angles and torsion angles while atomic co-ordinates appear in Table 2.Synthesis of [IrL JCPF I,.-The complex [IrHL,][PFp] (0.1 g 0.12 mmol) was dissolved in water (5 cm3) treated with concentrated HNO (1 cm3). The solution was stirred under reflux for 2 h and excess of NH4PF6 added to the cooled solution.The white precipitate was collected and washed with small amounts of water and MeOH and recrystallised from MeNO,-diethyl ether to afford [IrL,][PF,] as a colourless product in 70% yield (Found C 14.9; H 2.35. Calc. for C 14.6; H 2.45%). Infrared spectrum bands [IrL,][PF,], assigned to L and PF6- counter ion only. N.m.r. (CD,CN 298 K) 'H (80 MHz) 6 3.23 (m CH,); I3C (50.32 MHz) 1.8 1 8( 20) I .855(22) 1.54( 3) 1.786(21) 1.8 19( 19) 1.49( 3) 1.849(22) 1.836(21) 1.48( 3) 1.819(21) 1.788(21) 1.54(3) C(6)-S(7) S(7)-W C(8)-C(9) S(ll)-C(21) S( 11)-C(91) C(21)-C(31) C(3 1)-S(41) S(41 )-C(5 1) C( 5 1 )-C(6 1) C(61 )-S(7 1) S(71)-C(81) C(8 1)-C(9 1) 101.8(9) 11 1.9(13) 1 13.6( 13) 102.2(7) 106.4(7) 99.2(9) C(3)-S(4FC(5) S(4)-C(5tC(6) C( 5)-C( 6)-S( 7) Ir-S( 7)-C( 6) Ir-S( 7)-C(8) C(6)-S(7)-C(8) S(7FC(f9-C(9) S(1 )-C(9)-C(8) 113.8(14) 1 12.2( 14) 107.4(7) 112.7(6) 101.4(9) 113.6(14) Ir-S( 1 1)-C(21) Ir-S( 1 1)-C(9 1) C(21)-S(ll)-C(91) S(1 l)-C(21)-c(31) C(2 1)-c(3 1)-s(41) 115.4( 15) 10 1.5(7) I14.6(7) Ir-S(41)-C(3 1) Ir-S(41)-C(5 1) C(3 l)-s(4l)-c(51) 106.7(9) S(41)-C(5 1)-C(61) 123.1( 15) C( 5 1)-C(6 1 )-S( 7 1) 117.3( 15) C(61)-S(7 1)-C(81) 1 0 5 3 10) S(7 1 kC(8 1)-C(9 1) 119.3(14) S( 1 l)-c(9l)-c(81) 120.2( 13) - 134.8(13) 63.7(15) 53.6(16) 61.2( 15) - 132.1(14) 46.2( 17) 67.3( 15) - 136.5(15) 49.q 18) 134.6( 15) - 76.9( 16) -40.1(20) - 77.5( 17) 6 1.9(20) J.CHEM. SOC. DALTON TRANS. 1990 Table 2. Atomic co-ordinates with e.s.d.s for [IrHL,][PF6],~2MeN0 X Z Y 0.201 78(6) 0.097 2(6) 0.028 3 5 ) 0.2500 0.365 03(24) 0.253 2(3) 0.304 O(3) 0.246 8(3) 0.201 4(3) 0.403 3(5) 0.373 2(6) 0.001 6(5) 0.314 3(6) 0.216 6(10) 0.255(3) 0.059 3(3) 0.080 O(4) 0.102 8(13) 0.139 6(8) 0.016 5(9) 0.066 4( 12) 0.080 3( 18) 0.331 3(19) 0.186 6(24) 0.098 l(15) 0.342 l(23) 0.226 6(7) 0.024 6(8) 0.134 6(11) 0.419 9(3) 0.406 2( 12) 0.434 9( 13) 0.383 4(9) 0.302 3(19) 0.146 7(22) -0.045 6(18) -0.119 O(19) 0.146 l(20) 0.335 2(19) 0.320 3(9) 0.296 4(10) 0.287 9( 10) 0.397 l(11) 0.419 4(10) 0.359 9(21) 0.359 9(21) C ( 3 H 4 ) S(4)-C(5) C(5W(6) C(6)-S(7) S(7)-C(8) W)-C(9) 1.851( 11) 1.822( 12) 1.486( 17) 1.81 3( 13) 1.824( 12) 1.5 lo( 17) Ir-S( 1) Ir-S(4) Ir-S(7) S(l)-C(2) S( 1 K ( 9 ) C(2P33) 100.8(4) 10 1.9( 5 ) 114.4(9) 113.3(9) 104.3(4) 100.7(4) 103.2(6) 114.7(8) 113.0(8) S( 1 )-Ir-S(4) S( 1 )-Ir-S( 7) S(4)-Ir-S(7) Ir-S( 1)-C(2) Ir-S( 1)-C(9) C ( 2 H 1 K ( 9 ) SUW(2W(3) W)-C(3)-S(4) Ir-S(4)-C(3) 62.8(9) - 132.5(9) 52.0(10) - 135.7(8) 63.5( 10) 49.2( 1 1) - 132.3(9) 64.7(10) 48.5(11) = 25 OOO dm3 mol-' O.oo00 0.028 43(24) 0.094 75(25) 0.092 l(3) -0.098 3(3) - 0.094 04(25) -0.200 5(3) 0.139 2(4) 0.083 4( 17) 0.175 8(9) 0.111 2(11) 0.213 O(12) 0.089 l(9) 0.192 l(12) 0.836 8(3) 0.902 9( 1 1) 0.771 3(12) 0.109 7(10) 0.104 l(10) 0.185 7(10) 0.171 4(10) 0.134 8(11) 0.078 3( 11) Table 3.Bond lengths (A) angles and torsion angles (") with e.s.d.s for [IrL,][PF,] ,-5MeN0 2.342(3) 2.341(3) 2.338(3) 1.826( 12) 1.822(12) 1.487( 16) 88.28( 10) 89.1 l(10) 88.46( 10) 10 1.6(4) 104.2(4) 102.3(5) 113.3(8) 11 1.9(8) 104.0(4) 6 36.60 p.p.m. (CH,). Fast-atom bombardment mass spectrum (3-nitrobenzyl alcohol) m/z 843 697 and 551; cak. for ['931rL2(PF6)2]+ [1931rL2(PF6) - H] + and [Ig3IrL2 - 2H]+ 843 697 and 551 respectively. Electronic = 229 nm E,,,. spectrum (MeCN) A,,,. cm-'. X-Ray Structure Determination of [IrL2][PF6]3-5MeN02.- A colourless slightly flattened needle (0.15 x 0.39 x 0.58 mm) suitable for X-ray analysis was obtained by vapour diffusion of diethyl ether into a solution of the complex in MeNO,.Crystal data. C12H24F,81rP3S64MeN02 M = 1 292.8 monoclinic space group C2/c (no. 15) a = 8.581 7(13) b = X - 0.182 9( 10) -0.167 3(11) -0.141 4(11) -0.139 8(11) -0.135 4(11) -0.129 9(10) 0.820 6(20) 0.893 O( 15) 0.847 5(15) 0.778 l(14) 0.886 9(22) 0.884 l(20) 0.774 (17) 0.792 5(18) 0.527 5(15) 0.580 3( 1 1) 0.644 4( 10) 0.572 2(17) 0.480 7( 13) 0.417 6(15) 0.357 8( 14) 0.421 9(14) - 0.029(4) 21.338(4) c = 23.482(7) A p = 90.94(2)' U = 4 299 A3 [from 20 values of 24 reflections measured at fo (20 = 29-35' h = 0.71073 A)] Z = 4 (implying that each Ir lay on a two- fold special position) D = 1.997 g ~ m - ~ p = 3.608 mm-' 1763 0.221 4(10) 0.227 5( 11) 0.107 5(10) 0.065 4( 10) 0.107 7(10) 0.177 6(9) 0.452 O( 19) 0.494 3(14) 0.382 5(15) 0.350 4( 14) 0.479 l(20) 0.456 2(20) 0.342 7(16) 0.405 7( 18) 0.163 O(12) 0.154 3(10) 0.201 9(9) 0.085 3(15) 0.356 O( 1 1) 0.360 l(13) 0.310 8(12) 0.427 6( 13) 0.174(4) F(OO0) = 2544.Data collection and processing. Stoe STADI-4 four-circle diffractometer graphite-monochromated Mo-K X-radiation T = 298 K OF-20 scans with o scan width (1.05 + 0.347 tan0)o 2 9 14 unique data measured (20,,,. 45' h - 9 to 9 k (r- 22 1 0-25) giving 1916 with F 3 6 4 9 for use in all calculations.Slight isotropic crystal decay (ca. 9%) corrected for during data reduction no absorption correction. Structure solution and rejinement. The position of the Ir on an inversion centre was inferred from cell contents and intensity statistics subsequent iterative cycles of least-squares refinement and difference Fourier synthesis located all non-H atoms. Disorder in the PF6- anions was modelled by allowing partial occupation of alternative sites by some F atoms. Fully occupied non-H atoms were then refined (by least squares on q 2 O with anisotropic thermal parameters with macrocyclic H atoms included at fixed calculated positions and solvent H atoms as part of rigid groups. At final convergence R R' = 0.0403,0.05 1 1 respectively S = 1.047 for 284 refined parameters and the final A F synthesis showed no peak above 1.31 e A-3.The weighting scheme w-' = 02(F) + 0.00 955F2 gave satisfactory agreement analyses a secondary extinction parameter refined to 2.1(4) was 0.183. Table 3 and in the final cycle gives bond lengths angles and torsion angles while atomic co- ordinates appear in Table 4. x For both structure determinations atomic scattering factors were inlaid,20 or taken from ref. 22. Molecular geometry calculations utilised CALC 23 and the Figures were produced by ORTEP 11.24 Additional material available from the Cambridge Crystal- lographic Data Centre comprises thermal parameters. Acknowledgements We thank the S.E.R.C.for support and Johnson Matthey for generous loans of platinum metals. Y 0.278 3(20) 0.250 6(20) 0.071 l(21) -0.01 8(21) 0.138 8(20) 0.473 6(21) 0.522 2(19) 0.382(3) 0.067(3) 0.323(3) 0.366(3) 0.073(3) 0.202(3) 0.406(3) 0.187 4(22) 0.195 O(17) 0.176 8(16) 0.2 19( 3) 0.190 5(19) 0.204 4(21) 0.228 2(21) 0.209 5(23) 0.262(4) X o.oO0 0 -0.159 8(3) - 0.306 2( 13) - 0.238 6( 12) -0.106 9(3) 0.057 9( 13) 0.141 7(15) 0.190 7(3) 0.127 9(14) -0.045 6(15) o.Oo0 0 0.127 8( 11) 0.089 6( 16) 0.517 3(4) 0.385 6( 16) 0.647 O( 15) - 0.063 7( 17) 0.010 3( 16) 0.101 9(16) -0.008 7(22) 1764 Table 4 Atomic co-ordinates with e.s.d.s for [IrL2][PF,],*5MeN02 Atom References 1 A.J. Blake and M. Schroder Ado. Znorg. Chem. in the press. 2 M. Schriider Pure Appl. Chem. 1988,60,517. 3 S. R. Cooper Ace. Chem. Res. 1988,21,141. 4 M. N. Bell A. J. Blake H-J. Kiippers M. Schroder and K. Wieghardt Angew. Chem. 1987 99 253; Angew. Chem. Znt. Ed. Engl. 1987,26,250. 5 A. J. Blake R. 0. Gould A. J. Holder T. I. Hyde M. 0. Odulate A. J. Lavery and M. Schriider J. Chem. SOC. Chem. Commun. 1987,118. 6 K . Wieghardt M. Koppen W. Swiridoff and J. Weiss J. Chem. SOC. 7 A. J. Blake A. J. Holder T. I. Hyde Y. V. Roberts A. J. Lavery and Dalton Trans. 1983 1869. M. Schroder J. Organomet. Chem. 1987,323,261; A. J. Blake A. J. Holder T. I. Hyde and M. Schroder J. Chem. SOC. Chem. Commun. 1987,987. 8 A. J. Blake L.M. Gordon A. J. Holder T. I. Hyde G. Reid and M. Schroder J. Chem. SOC. Chem. Commun. 1988 1452; A. McAuley T. W. Whitcombe and G. Hunter Znorg. Chem. 1988,27 2634; A. McAuley and T. W. Whitcombe ibid. p. 3090. 9 A. J. Blake R. 0. Gould A. J. Holder T. I. Hyde and M. Schroder J. Chem. SOC. Dalton Trans. 1988,1861; S. C. Rawle R. Yagbasan K. Prout and S. R. Cooper J. Am. Chem. SOC. 1987,109,6181. 10 A. J. Blake T. I. Hyde and M. Schroder J. Chem. SOC. Dalton Trans. 1988,1165. 11 See for example M. D. Farnos B. A. Woods and B. B. Wayland J. Am. Chem. SOC. 1986,108,3659; K. J. Del Rossi and B. B. Wayland J. Chem. SOC. Chem. Commun. 1986 1653; J. P. Collman and K. Kim J. Am. Chem. SOC. 1986,108,7847. 12 R. D. Hancock and A. E. Martell Comments Znorg.Chem. 1988,6 237. Y o.Oo0 0 0.087 04(13) 0.054 2(6) 0.014 4(5) - 0.046 49( 1 3) -0.041 9(6) 0.019 O(6) 0.045 28(14) 0.126 9(5) 0.136 3(5) 0.149 71(24) 0.148 O(5) 0.102 l(8) 0.248 33(16) 0.262 5(8) 0.230 5(7) 0.405 7(6) 0.381 3(6) z 0.500 0 0.482 35(12) 0.433 6(5) 0.388 2(4) 0.417 93(12) 0.370 2(5) 0.371 6(5) 0.443 ll(12) 0.442 9(5) 0.435 3(5) 0.250 0 0.299 6(4) 0.217 7(6) 0.409 13(16) 0.452 O(6) 0.369 l(6) 0.037 8(7) 0.075 2(7) 0.105 5(7) 0.084 8(8) 0.409 6(7) 0.313 6(7) X 0.587(3) 0.381(4) 0.496(4) 0.487(4) 0.648(4) J. CHEM. SOC. DALTON TRANS. 1990 0.51 1 O(20) Y 0.047 O( 10) 0.073 l(19) 0.141 O(14) 0.500 0 0.500 0 0.176 5(24) 0.245 6( 17) 0.3 17(3) 0.385 O(7) 0.383 l(8) 0.426 2( 10) 0.323 6( 11) 0.177 4(13) 0.214 4(11) 0.254(3) 0.119(3) 0.060( 3) 0.454 6(25) 0.614(3) 0.6 lO(5) 0.180 4(10) 0.212 O(14) 0.303 3( 18) 0.271 7(15) 0.225 O(18) 0.306 5( 15) 0.179 6(15) 0.249 4(22) 0.318 3(16) 0.31 1 4(19) 0.202 4(8) 0.250 0 0.250 0 0.312 4(7) 0.270 l(6) 0.53 5( 5 ) 0.631(6) 13 R.S. Glass G. S. Wilson and W. N. Setzer J. Am. Chem. Soc. 1980 102 5068. 14 K. Wieghardt H-J. Kiippers E. Raabe and C. Kruger Angew. Chem. 1986,98 1136; Angew. Chem. Int. Ed. Engl. 1986,25 1101. 15 A. J. Blake R. 0. Gould J. A. Greig A. J. Holder T. I. Hyde and M. Schroder J. Chem. Soc. Chem. Commun. 1989,876. 16 H-J. Kuppers A. Neves C. Pomp D. Ventur K. Wieghardt B. Nuber and J. Weiss Znorg. Chem. 1986,25,2400. 17 A. J. Blake A. J. Holder T. I. Hyde H-J. Kuppers M. Schroder S. Stotzel and K. Wieghardt J. Chem. SOC. Chem. Commun. 1989,1600. 18 N. Serpone and M. A. Jamieson in ‘Comprehensive Co-ordination Chemistry,’ eds. G. Wilkinson R. D. Gillard and J. A. McCleverty Pergamon Oxford 1987 vol. 4 ch. 49 p. 1097. 19 DIFABS program for empirical absorption corrections N. Walker and D. Stuart Acta Crystallogr. Sect. A 1983,39 158. 20 SHELX 76 program for crystal structure refinement G. M. Sheldrick University of Cambridge 1976. 21 A. J. Blake R. 0. Gould G. Reid and M. Schroder J. Organomet. Chem. 1988,356,389. 22 D. T. Cromer and J. L. Mann Acta Crystallogr. Sect. A 1968 24 321. 23 CALC program for molecular geometry calculations R. 0. Gould and P. Taylor University of Edinburgh 1985. 24 ORTEP 11 interactive version P. D. Mallinson and K. W. Muir J. Appl. Crystallogr. 1985 18,51. Received 1 lth October 1989; Paper 9/04385C Z 0.255 3(8) 0.238 9( 1 1) 0.208 6( 1 1) 0.227 7(9) 0.393 2( 11) 0.456 O(8) 0.443 3( 19) 0.359 8( 10) 0.370 7( 13) 0.364 5(13) 0.435 5(18) 0.459 4( 13) 0.419 O(19) 0.402 7(22)
ISSN:1477-9226
DOI:10.1039/DT9900001759
出版商:RSC
年代:1990
数据来源: RSC
|
|