摘要:

1979 287Side-bonded Ketone Complexes of Platinum(0). Indan-l,2,3-trione Com-plexes ; Molecular and Crystal Structure of [2,2',-Bis(indan-l,2,3-trio-nato) (2-)-0202'] bis(triphenylphosphine)platinumBy Martin M . Hunt, Raymond D. W. Kemmitt," David R. Russell," and Paul A. Tucker, Department ofChemistry, The University, Leicester LE1 7RHReactions of equimolar quantities of [PtL,] (L = PPh, or AsPh,) with either indan-1.2.3-trione (int) or 2,2-di-hydroxyindan-I ,3-dione afford the side-bonded ketone complexes [Pt(int) L,] which undergo ring-expansion re-actions with int to give [Pt((int),}L,]. Crystals of the adduct [Pt((int),)(PPh,),] are monoclinic, space group Ccwith a = 22.08, b = 14.47, c = 30.72 A, (3 = 95.1 ", and Z = 8. Least-squares refinement of the structural para-meters reduced R to 0.078 for 2 382 reflections.The adduct has the two indan-1.2.3-trione moieties linked via thecarbon atoms of the central carbonyl groups and bonded by the oxygen atoms a t these groups to the platinum togive a five-membered 1.3-dioxa-2-platinolan ring. Ring-expansion reactions of [Pt(int)L,] and ring-substitutionreactions of [Pt((int),}L,], with hexafluoropropan-2-one and hexafluorobut-2-yne are also described. Re-actions with hexafluoropropan-2-one give both five- and seven-membered ring systems. The side-bonded com-plexes [Pt(int) La] react with dioxygen to give cyclic dicarboxylato-complexes.ALTHOUGH hexafluoropropan-2-one is known to co-ordinate to low-valent metal complexes via its P,,-p,,orbitals,l examples of other ketones behaving in thismanner are restricted to certain a, p-unsaturatedketones,2-6 which act as bidentate ligands, and thefluoroketones, chloropentafluoropropan-2-one,6 1,3-di-chlorotetrafluoropropan-2-one,6 and CF,COCN.' Afeature of fluorinated ketones is the electrophilic be-haviour of the carbonyl group and we wished to investi-gate the organometallic chemistry of the electrophilicketone indan-1,2,3-trione [int,(l)],* in particular thepossibility of ring-opening reactions.We had previ-ously discovered that platinum(o) causes ring opening ofbenzocyclobutene- 1,2-dione .g0@=o0( 1 1 intRESULTS AND DISCUSSIONTreatment of a benzene solution of tetrakis(tripheny1-phosphine)platinum(o) with an excess of indan-1,2,3-Ph PPh3P''Ptrione (1) gave a yellow complex of formula [Pt((int),}-(PPh,),] (2). In order to clarify the exact nature of (2)a single-crystal X-ray diffraction study was carried outthereby establishing (2) as the five-membered ringcomplex.The molecular geometry and atom numbering areillustrated in Figure 1.The two molecules in the asym-metric unit have almost identical geometries. The largeestimated standard deviations (e.s.d.s) prohibit detailedMolecule 2Molecule 1FIGURE 1 Molecular geometry and atom numbering for the twomolecule288discussion of bond lengths and angles (listed in Table 1)but the mean values are unexceptional.The co-ordination about platinum is planar to withinexperimental error for both molecules. The Pt-O-C-C-0ring is non-planar in both molecules, the carbon atomsbeing on the same side (but at different distances) of theplane defined by the platinum and oxygen atoms. ThisJ.C.S.Dalton0.4 A on average from the mean plane of the other fourcarbon atoms and the oxygen atoms of the two ketonicgroups 0.2 A on the opposite side of this plane.It is apparent from Figure 1 that a head-to-taillinkage of the ketones, structure (3), would bring theindantriketone moiety adjacent to the platinum intoclose proximity with the phenyl groups of the triphenyl-Pt-P( 1)Pt-P(2)P( 1)-C(31)P(l)-C(41)P( 1)-C(51)P(2)-C(61)P (2) -C (7 1)P( 2)-C( 81)Pt-O(1)C(2)-0(2)C(3)-0(3)C(5)-0(5) c (6)-0 (6)W)-O( 1)C(4)-0(4)C( 1)-C(4)C ( 1 )-c (2)c (4)-c (5)C(4)-C(6)C(2)-C( 11)Pt-0 (4)C ( 1)-C(3)C (3)-C( 12)C (5)-C ( 2 1)C ( 6) -C ( 22)TABLE 1Bond lengths (A) and angles (") *Molecule 1 Molecule 22.30 2.15 P( 1)-Pt-P(2)2.25 2.16 P(1)-Pt-O(1)mean 2.22(7) P(2)-Pt-0(4)1.81 1.84 0 (1 )-Pt-0 (4)1.82 1.811.80 1.95 Pt-O( 1)-C(1)1.77 1.77 P t-0 (4)-c (4)1.80 1.731.93 1.93 O( 1)-C( 1)-C(4)mean 1.83(7) 0 (4) -C (4)-C ( 1)2.15 2.05mean 2.06(7)1.32 1.282.05 1.97 c (2)-c (1)-c (3)1.11 1.14 C( l)-C(2)-C( 11)1.30 1.06 c ( 1 )-c (3)-c ( 1 2)C (5)-C (4) -C (6)1.42 1.22 C( 14)-C(5)-C(21)mean 1.23(12)1.54 1.43C (4) -C (6)-C (22)1.28 1.38 c (2)-C( 1 I)< ( 1 2)C( 3)-c (1 2)-c ( 1 1) mean 1.41(11)1.73 1.41 C( 5)-C (2 1)-C (22)C (6)-C (2 2)-C (2 1) mean 1.571.69 1.601.66 1.761.38 1.531.44 1.45mean 1.56(13)1.46 1.511.58 1.371.50 1.561.58 1.44mean 1.50(7)C(l)-C(2)-0(2)C(l1)-C(2)-O(2)C( 1)-C(3)-0(3)C ( 12)-C (3)-0 (3)C (4)-C (5)-0 (5)C( 2 1)-C (5)-0 (5)C (4)-C (6)- (6)C( 22)-C (6)-0 (6)Molecule 1 Molecule 2102 9392 8785 10083 8097 108118 112mean 109(9)106 115102 108mean 108(5)107 104102 103mean 104(2)101 10294 103118 103110 111mean 105(7)119 115110 I15106 109103 107mean 11 l(6)137 118123 128117 124148 120130 127112 129125 131120 116mean 125(8)* Individual e.s.d.s are 0.03 for Pt-P, 0.04 for Pt-0, 0.07 for P-C, and 0.09 A for C-C and C-0.lndividual e.s.d.s for the angleslie between 5 and 8"conformation achieves a staggering of the indan-1,2,3-trione residues as illustrated in Figure 2.The five-FIGURE 2 Relative orientation of the two indantrione residuesmembered ring of each indan-l,2,3-trione residue is non-planar with the carbon atom linking the two residuesfor molecule 1. Molecule 2 is similarphosphine ligands and this may be a reason why thehead-to-head linking of the two trione molecules ispreferred in this system. In similar reactions involvinghexafluoropropan-2-one only head-to-tail linkage of thisketone has been observed.1°The formation of (2) may proceed via co-ordination ofthe central, most electrophilic, carbonyl group of indan-1,2,3-trione to the platinum to give (4), followed by ringexpansion of the three-membered ring, a processanalogous to that proposed for the ring expansion ofsimilar complexes of hexafluoropropan-2-0ne.~~ Evi-dence that this mechanism operates in the formation of(2) is provided by the observation that treatment o1979 289[Pt(PPh,),] with an equimolar quantity of indan-1,2,3-trione gave a complex [Pt(int)(PPh,),] (4) which reactswith a further equimolar quantity of indan-l,2,3-trioneto give (2).The physical and chemical properties of (4)strongly support a structure in which the central carbonylgroup of the trione is co-ordinated to platinum via its$,,-p,, orbitals as is found in [Pt{OC(CF,),)(PPh,),] .lThus the i.r. spectrum of (4) exhibits two carbonylabsorptions at 1709 and 1678 cm-l, typical of the COgroups of indan-1 ,3-dione.11J2 Furthermore, the form-ation of (4) would be consistent with the observationthat indan-l,2,3-trione is known to act as a dienophile inDiels-Alder reactions.12The side-bonded indan-1,2,3-trione complex (4) mayalso be obtained by reaction of the diol (5) with00( 5 1[Pt(PPh,),] as well as by the reactions of (1) or (5) witheither [Pt(tram-PhCH=CHPh) (PPh,),] or [Pt(PhC-CPh)(PPh,),].It is surprising that both (1) and (5) formthe same three-membered ring complex (4) and thisobservation suggests that PtO is a powerful enough nucle-ophile to displace water from the diol (5). However,reactions with (5) were approximately four times slowerthan with indan-1,2,3-trione.The reactions of [Pt(AsPh,),] with the appropriatequantity of (1) gave the triphenylarsine derivatives of(2) and (4).The triphenylarsine ligands in [Pt(C,F,)-(AsPh,),] are readily displaced by tertiary phosphines.l3However, only intractable red oils or solids were ob-tained by treating [Pt(int) (AsPh,),] with either 1,2-bis-(dipheny1phosphino)ethane or methyldiphenylphosphine.The indan-l,2,3-trione ligand in (4) was readily dis-placed by hydrogen chloride gas and tetrachloro-o-benzo-quinone to give cis-[PtCI,(PPh,),] and [Pt (O,C,CL,)-(PPh,),] respectively. When stored under dinitrogen,complex (4) was indefinitely stable but in the atmosphereit reacted slowly with dioxygen and its yellow colourfaded. In benzene solution the reaction of dioxygenwith (4) was rapid and elemental analyses and molecular-weight data for the white crystalline product indicatethe formation of a 1 : 1 adduct (6).The complexexhibits strong carbonyl absorptions at 1752 and 1 675cm-l and strong absorptions at 1315 and 1275 cm-l.The same complex (6) could be isolated from the reactionbetween (1) and [PtO,(PPh,),], and surprisingly from thereaction between the diol (5) and [PtO,(PPh,),]. Thisone complex (6) isolated from these three reactions mightbe expected to have a five-membered ring structureinvolving a peroxy-group analogous to the systemsformed with aldehydes and ketones.l49l5 However, ithas been shown that a-diketones, when involved in thistype of five-membered ring structure, rearrange to givedicarboxylato-complexes.16 By analogy, it seems reason-able to expect indan-1,2,3-trione to undergo a similarreaction to yield the dicarboxylato-complex (6) via anunstable five-membered peroxy-ring complex (Scheme).The strong absorptions in the i.r.spectrum at 1315 and1 275 cm-l can be assigned to v,,,(OCO) for the carboxyl-ato-complex (6) ; these fall in the region characteristicof carboxylate groups bonded to p1atin~m.l~ Anabsorption at 1 675 cm-l can be assigned to v,,(OCO).Further evidence for the formulation of (6) as a carb-oxylato-complex rather than a five-membered peroxy-ring complex is provided by the observation that (6) canbe recovered unchanged after refluxing a suspension ofthe complex for 1 d in isopropyl alcohol. Similarly,dioxygen reacts with [Pt(int)(A~Ph,)~] to give a carb-oxylato-complex analogous to (6).In the mechanism we propose for this reaction(Scheme), two different intermediate five-memberedperoxy-ring systems, (A) and (B), initially form, whichcan both collapse to the same carboxylato-complex (6).The reaction of dioxygen with (4) presumably proceedsvia (A).However, it seems more likely that reactionsinvolving the diol (5) proceed via formation of a fi.;e-membered peroxy-ring intermediate involving a carbonylgroup adjacent to the aromatic nucleus. This inter-nL ,PtOO + Oho- \ /( A )1 f0( B ) ( 6 )SCHEME L = PPh, or AsPh,mediate would then dehydrate to give (B) which collapsesto (6). In these reactions we have not observed theformation of an intermediate peroxy-ring system. Thismay be a steric effect since it is known that bulky sub-st i t uen t s enhance the format ion of carbox ylat o-com-plexes.16Although complex (4) readily undergoes a ring-expansion reaction with indan-1,2,3-trione this is notthe case with propan-2-one or fluoren-9-one.However,when (4) was treated with hexafluoropropan-2-one atroom temperature in benzene two products were isolated.The major product was a yellow crystalline air-stablesolid. Microanalytical and molecular-weight data indi-cate a 1 : 1 adduct (7) between (4) and hexafluoro290 J.C.S. Daltonpropan-2-one. The i.r. spectrum of (7) shows a strongabsorption in the carbonyl region at 1705 cm-l andweaker absorptions a t 1760 and 1733 cm-l. The 19Fn.m.r. spectrum shows one singlet. The data are con-sistent with a structure in which the two ketones arepresent in a five-membered ring system.The absenceof 31P and lg5Pt splitting in the 19F n.m.r. spectrumindicates carbonyl oxygen-platinum bonding for thehexafluoropropan-2-one and, in view of the structurefound for (2), structure (7) is proposed for this 1 : 1adduct. Treatment of (7) with hydrogen chloride gasor trifluoroacetic acid gave cis-[PtCl,(PPh,),] and[Pt(O,CCF,),(PPh,),] respectively. However, withfive-membered ring followed by recombination to givethe observed product. The observation that un-changed (7) and a low yield of [Pt{OC(CF,),}(PPh,),]could be isolated from the reaction mixture is in agree-ment with this suggestion. The five-membered ringcomplex (7) appears to be more reactive towards hexa-fluoropropan-2-one than is [bt{OC(CF,),Ob)(PPh,),],since this last dioxygen ring complex does not undergofurther ring expansion with hexafluoropropan-2-0ne.l~The reaction of (4) with hexafluorobut-2-yne at 60 "Cled to displacement of the ketone and formation of[Pt (CF,CXCF,) (PPh,),]. However, at room temper-ature three products were formed: (2), [Pt(CF,CfCCF,)-(PPh,),], and a 1 : 1 adduct between (4) and the acetylene.The i.r.and 19F n.m.r. data for this latter complex areconsistent with a five-membered ring structure andassuming that the ketone again forms a platinum-oxygen bond in the ring then the structure (9) can behydrochloric acid, (7) gave cis-LPtCl,(PPh,),] and theoxygen adduct (6).The second product, (S), isolated from the reaction ofhexafluoropropan-2-one with (4), was a white crystallinesolid for which elemental analyses suggest a 1 : 2 adductbetween (4) and hexafluoropropan-2-one. The i.r.spectrum shows a strong absorption in the carbonylregion at 1 732 cm-l and the l9F n.m.r.spectrum containsfour quartets centred at 5.98, 7.98, 15.6, and 17.8 p.p.m.each showing approximately equal 19F-19F coupling. Itseems probable that this adduct contains a seven-membered ring, the absence of 31P and Ig5Pt coupling inthe 19F n.m.r. spectrum again implying the absence ofplatinum-carbon bonding of the hexafluoropropan-2-one.Puckering of the seven-membered ring would rendereach CF, group non-equivalent and the gem-CF, groupscan thus couple to give the observed quartets in thel9F n.m.r.spectrum. Complex (8) may have a structure(8a) analogous to that found for the seven-memberedring formed from [Pt(O,) (PPh,),] and hexafluoropropan-2-0ne.l~ However, structure (8b) would also be con-sistent with the 19F n.m.r. data and confirmation of thestructure must await additional data.Treatment of (7) with hexafluoropropan-2-one at70 "C also gave a low yield of the seven-membered ringcomplex (8). This would appear to be a novel five- toseven-membered ring-expansion reaction. However, itis possible that the reaction goes via dissociation of theassigned to this complex. The complex [Pt(int)-(AsPh,),] undergoes a much more rapid reaction withhexafluorobut-2-yne than does (4).However, theonly two products which could be isolated were [Pt-(CF,C-CCF,) (AsPh,),] and the triphenylarsine derivativeof (2). These reactions with hexafluorobut-2-yne thuslead to some displacement of the triketone from theplatinum, in contrast to the reactions observed withhexafluoropropan-2-one in which no simple displacementproducts were oh t ained.Our observation that hexafluoropropan-2-one would' ring expand' (7) to (8) prompted an investigation ofthe reactions of the five-membered ring system (2) withhexafluoropropan-2-one and hexafluorobut-2-yne. Atroom temperature (2) reacted with hexafluoropropan-2-one to give (l), (7), and (8) together with a smallamount of a complex which appears to be another 1 : 1adduct of (4) with hexafluoropropan-2-one.However,this product is not identical to (7). I t may be an isomerof (7) in which there is head-to-tail linking of the carbonylgroups in the five-membered ring. Insufficient materialand low solubility precluded a 19F n.m.r. study. Incontrast, hexafluorobut-2-yne did not react with (2) atroom temperature but at 60 "C both molecules of indan-1,2,3-trione were displaced from the platinum and[Pt (CF,C-CCF,) (PPh,),] was isolated.The results described in this paper indicate that otherelectrophilic ketones besides hexafluoropropan-2-one canform side-bonded complexes with PtO. The presentindan-l,2,3-trione complexes, however, are considerablymore reactive than the hexafluoropropan-2-one com-plexes of Pto so far described.This increased reactivit1979 291of indan-l,2,3-trione complexes is probably a conse-quence of steric effects and the poorer x-acceptingability of indan-l,2,3-trione as compared to hexa-fluoropropan-2-one, factors which would weaken theattachment of indan-l,2,3-trione to PtO. Indeed, un-like hexafluoropropan-2-one,l we find that (1) does notform an adduct with trans-[IrCl(CO) (PPh,),].EXPERIMENTALMelting points (Table 2) were measured on a Reicherthot-stage apparatus and are uncorrected. Infrared spectrawere recorded using Nuj ol and hexachlorobutadiene mullson a Perkin-Elmer model 225 spectrophotometer betweenKBr (400-4 000 cm-l) and Polythene (200-400 cm-l)plates. Fluorine-19 n.m.r. spectra were obtained a t 56.4MHz on a Varian Associates DAB0 instrument, lH spectraa t 60 MHz on a Varian Associates TGO instrument.Mole-cular-weight determinations were carried out by BellerMikroanalytisches Laboratorium and microanalyses byPascher Mikroanalytisches Laboratorium (Table 2).each case a yellow, rather than dark brown, solution wasproduced during the reaction.Tetrakis (triplTzenylphosphine)platinum((,) with an equimolarquantity of ninhydrin. The complex [Pt(PPh,),] (1 g, 0.8mmol) and ninhydrin (0.14 g , 0.8 mmol) were stirred to-gether in benzene (100 em3) for 2 h to produce a dark brownsolution. The volume of the solution was reduced (ca.20 cm3) by evaporation under reduced pressure and anexcess of diethyl ether (ca. 100 cm3) was added. Yellowcrystals were slowly deposited which were filtered off,washed with diethyl ether, dried in vacuo, and stored undernitrogen.These were shown to be (4) by their m.p. 212-220 "C (decomp.), i.r. spectra, and microanalysis (Found :C, 61.5; H, 3.7%).As with indan- 1,2,3-trione, ninhydrin reacted with[Pt(trans-PhCH=CHPh) (PPh,),] and [Pt(PhC-CPh) (PPh,),]to give (4).Tetrakis(triPhenylarsine)platinum((,) with an equimolarquantity of indan-1,2,3-trione. The complex [Pt(AsPh,),](2 g, 1.4 mmol) and indan-1,2,3-trione (0.2 g, 1.4 mmol)were stirred together in benzene (150 cm3) for 1 h. TheTABLE 2Melting points, yields, and microanalytical data for the complexes(0, I "C)210-214149-1 5 1157-161152-156168-17 1230-240210-220182-185164-168Yield858468616076622611(%)Foundr - iC H61.3 4.156.5 3.861.6 4.358.3 3.858.8 4.053.9 3.755.0 3.450.7 2.956.7 3.3- 0'6.85.59.68.48.78.0cefAnalysis (%)A-C H61.5 3.955.8 3.562.4 3.757.5 3.459.3 3.854.1 3.455.2 3.350.5 2.856.4 3.3Calc.05.45.09.28.58.89.0-h---M "893 (880)970 (968)1 030 (1 040)1135 (1 128)1020 (912)1 078 (1 000)1 020 (1 046)1203 (1 212)951 (1 042)a Molecular weights determined osmometrically in CHC1, ; calculated values are given in parentheses.With decomposition.F, 10.7 (requires 10.9%). Gas evolved with decomposition. F, 18.3 (requires 18.8%). f F, 11.1 (requires 10.9%).Indan- 1,2, 3-trione,ls [Pt( PPh,),] ,la [Pt (AsPh,),],ls [Pt-(trans-PhCH=CHPh) (PPh,),],20 [Pt(PhCECPh) (PPh,),],21[Pt0,(PPh,),],22 and trans-[IrCl(CO) (PPh,),] 23 were pre-pared as described in the literature.The light petroleumused had b.p. 30-40 "C. All the reactions were carriedout in a dinitrogen atmosphere unless otherwise stated.Reactions .-Tetrakis (tripheny1phosphine)~latinum (0) withan equimolar quantity of indan- 1,2,3-trione. The complex[Pt(PPh,),] (1 g, 0.8 mmol) and indan-lJ2,3-trione (0.13 g,0.8 mmol) were stirred together in benzene (100 cm3) for30 min to produce a dark brown solution. The volume ofthe solution was reduced (to ca. 20 cm3) by evaporationunder reduced pressure and an excess of diethyl ether(100 cm3) was added. Yellow crystals of (indan-1,2,3-trione) bis( tripheny1phosphine)platinum ( 0 ) (4) were slowlydeposited.These were filtered off, washed with diethylether, dried in vacuo, and stored under nitrogen. Yield0.6 g (85%); v(C=O) a t 1 709m and 1 678s cm-l.The same general method was used for the reactions of(trans-stilbene)bis(triphenylphosphine)platinum(o) ( 1 g, 1.1mmol) and (diphenylacetylene) bis(tripheny1phosphine)-platinum(0) (1 g, 1.11 mmol) with indan-l12,3-trione (0.18 g,1.1 mmol and 0.18 g, 1.1 mmol respectively) to yield ineach case (4) (0.8 g, 81% and 0.76 g, 73% respectively). Inresulting clear yellow solution was reduced in volume (ca.50 cm2) by evaporation under reduced pressure andan excess of diethyl ether (ca. 150 cm3) was added.Yellow crystals of (indan- 1,2,3-trione)bis(triphenylarsine)-platinum(0) were slowly deposited.These were filteredoff, washed with diethyl ether, dried in vacuo, and storedunder nitrogen; v(C=O) at 1712m and 1684s cm-l. Thecomplex, unless stored under nitrogen, turned brown-yellow after several days.Similarly, the reaction of [Pt(AsPh,) with ninhydringave [Pt(int) (AsPh,),].Of (indan- 1,2,3-trione)bis(triphenyl~hos~hine)platinum(o)(4). (a) With indan-l12,3-trione. Complex (4) (0.25 g,0.28 mmol) and indan-l12,3-trione (0.055 g, 0.29 mmol)were stirred together in benzene (20 cm3) for 48 h. Theresulting bright yellow solution was filtered and reduced involume (ca. 10 cm3) by evaporation under reduced pressure.Slow addition of diethyl ether gave yellow crystals (prisms)of [Pt{ (int),)(PPh,),] (2) which were filtered off, washed withdiethyl ether, and dried in vucuo.( b ) With hydrogen chloride. Hydrogen chloride gas waspassed through a solution of (4) (0.5 g, 0.56 mmol) inbenzene (50 cm3) for 5 min.The white suspension wasfiltered off and another crop of the white solid was obtaine292by reducing the volume of the filtrate by evaporationunder reduced pressure. Recrystallisation of the whitesolid from methylene chloride-ethanol gave white crystalsof cis-dichlorobis(triphenylphosphine)platinum(II) (0.39 g,90%) identified by i.r. and m.p. 306-310 "C (lit.,24 310-312 "C).(c) With 3,4,5,6-tetrachZoro-o-benzoquinone. Complex (4)(0.25 g, 0.28 mmol) was stirred with 3,4,5,6-tetrachloro-o-benzoquinone (0.07 g, 0.28 mmol) for 12 h.The yellow-orange solution was filtered and reduced in volume (ca.10 cm3) by evaporation under reduced pressure. Additionof ethanol precipitated a yellow solid which upon re-crystallisation from methylene chloride-ethanol gave yellowcrystals of [Pt(O,Cl,ClJ (PPh,),] (0.24 g, 88%) identifiedby i.r. and m.p. 240 "C (lit.,25 246 "C).A suspension of (4) (0.8 g, 0.9 mmol)in oxygenated benzene (100 cm3) was shaken for 5 d. Thewhite suspension was filtered off, washed with a smallportion of benzene, and recrystallised from methylenechloride-benzene-diethyl ether to afford white needles of a1 1 adduct between dioxygen and (4) (0.5 g, 60%). Infra-red spectrum: 1752s [v(C=O)], 1675s [v(OCO)], 1583vw,1568vw, 1480m, 1438s, 1433s, 1315m [v(OCO)], 1 298vw,1275s [v(OCO)], 1231w, 1 188w, 1 158w, 1 147vw, 1 113w,1095s, 1072w, 1028vw, 1008w, 859m, 848w, 819w, 807vw,776vw, 766m, 760m (sh), 758m, 748m, 720m, 712m,706m (sh), 696% 662vw, 634vw, 624vw, 560m, 544m,532s, 527m (sh), 517m, and 512s cm-l.(e) With.hexafluoropropan-2-one. Hexafluoropropan-2-one (ca. 1.5 cm3) was condensed into a Carius tube (- 196 "C)containing (4) (0.7 g, 0.8 mmol) suspended in benzene(25 cm3). The tube was sealed and shaken a t room tem-perature for 3 d . The resulting pale yellow solid wasfiltered off and washed with diethyl ether and two morecrops of the pale yellow solid were obtained by evaporationof the filtrate under reduced pressure followed by additionof diethyl ether. The three crops were combined and re-crystallised from methylene chloride-diethyl ether to yieldpale yellow crystals of [Pt(OC(CF,),*int}(PPh,),I (7). Thesewere filtered off, washed with diethyl ether, and driedin vacuo.Yield 0.5 g (62%); v(C=O) at 760vw, 1 733m,and 1705s cm-l. The lgF n.m.r. spectrum in CH,Cl,exhibited a singlet at 7.1 p.p.m. relative to internal a,a,a-trifluorotoluene.The solvents from the filtrate and ether washings werecompletely removed by evaporation under reduced pressureand diethyl ether was added to the residue. A cream solidslowly precipitated from the solution and precipitation wascompleted by slow addition of light petroleum. Theprecipitate was recrystallised from methylene chloride-methanol to give white crystals (prisms) of [Pt(2 OC(CF,),-int}(PPh,),] (8).These were filtered off, washed withmethanol, and dried in vacuo. Yield 0.26 g (26?/,) ; v(C=O)at 1 732 cm-1. The 19 F n.m.r. spectrum in CH,Cl, showedfour signals at 6 5.98 [3 F, q, J(FF) 10.51, 7.98 [3 I;, br q,J(FF) ca. 10.51, 15.6 [3 F, q, J(FF) 10.51, and 17.8 p.p.m.[3 F, q, J(FF) 10.5 Hz] relative to internal C6H&F3.Hexafluorobut-2-yne (ca. 2 cm3) was condensed into a Carius tube (- 196 "C)containing (4) (0.25 g, 0.3 mmol) suqended in benzene(20 cm3). The tube was sealed and shaken at 60 "C for1 d. The solvent was removed under reduced pressure.The residue was dissolved in diethyl ether and the solutionwas filtered and reduced in volume. Addition of lightpetroleum gave white crystals of [Pt(C,F,) (PPh,),] (0.15 g,(d) With dioxygen.(g) With hexafiluorobut-2-yne at 60 "C.J.C.S.Dalton60y0), m.p. 212 "C (lit.,26 215-216 "C); v(CX) a t 1762s,cm-l (lit.,2s 1 775 cm-l).Hexa-fluorobut-2-yne (ca. 2 cm3) and (4) (1 g, 1 mmol) suspendedin benzene (ca. 25 cm3) were shaken in a Carius tube a t roomtemperature for 2 months. The resulting yellow solid wasfiltered off, washed with diethyl ether, and recrystallisedfrom methylene chloride-diethyl ether. The bright yellowcrystals (0.35 g, 30%) were identified as (2), m.p. 160-162 "C; v(C=O) a t 1 743m, 1 728vw, and 1 706s cm-l.Evaporation of the filtrate and ether washings underreduced pressure afforded a pale yellow residue. Theresidue was dissolved in niethylene chloride and additionof methanol and slow evaporation under reduced pressuregave a pale yellow solid which was filtered off and washedwith light petroleum.Recrystallisation from methylenechloride-methanol gave white crystals of [Pt (C,F,) (PPh,) ,](0.25 g, 25y0), m.p. 214 "C, v(C=C) at 1 762s c1n-l.The filtrate and petrol washings were slowly evaporatedunder reduced pressure to give a yellow solid which wasfiltered off. Recrystallisation from benzene-diethyl ether-light petroleum gave yellow crystals (needles) of [Pt-(CF,C=CCF,.int)(PPh,),] (9) (0.13 g, 11%). Infraredspectrum: 1751w, 1744w, 1738vw (sh), 1718s, 1704s,1 604w, 1 598w, 1 587w, 1 482m, 1 440s, 1 436m (sh),1344vw, 1307w (sh), 1298m, 1288m, 1281w, 1242s,1233s, 1182w (sh), 1 178m, 1160s, 1 136m (sh), 1 125,1 115m (sh), 1 lOOs, 1088m (sh), 1028vw, 1016vw, 994m,921vw, 856vw, 838w, 820w, 774w, 768w, 762m, 756m,749s, 743m, 732w, 712s, 703s, 697s (sh), 640w (sh), 636m,628, 548m, 536s, 531s, 527s, and 506m cm-l.The lSFn.m.r. spectrum in CH,Cl, showed two signals a t 6 -7.0513 F, q, J(FF) 15 Hz] and -13.6 p.p.m. (3 F, m) relative t ointernal C6H,CF3.(Indnn-1,2,3-trione)bis(tri~henylarsine)~latinum(o). (a)With indan- 1,2,3-trione. As for the corresponding tri-phenylphosphine complex, indan- 1,2,3-trione (0.04 g, 0.2mmol) and [Pt(int)(AsPh,),] (0.2 g, 0.2 mmol) gave after4 h yellow crystals of [Pt{(int),}(AsPh,),] (0.15 g, 61%);v(C=O) at 1 745m, 1 733vw, and 1 711s cm-l.(b) With dioxygen. A suspension of [Pt(int) (AsPh,),](0.8 g, 0.86 rnmol) in oxygenated benzene (100 cm3) wasshaken for 1 week.The white crystalline suspension wasrecrystallised from methylene chloride-diethyl ether and(f) With hexa~7uorobut-2-yne at room temperature.gave white needles of [~t{0,C*o-C,H4*C(0)~0,}(AsPh,)] (6;L = AsPh,) (0.65 g, 76%). Infrared spectrum: 1 755s[v(CO)], 1 679s [v(OCO)], and 1 313m cm-l [v(OCO)].(c) With hexafluorobut-2-yne. Hexafluorobut-2-yne (ca.2 cm3), [Pt(int)(AsPh,),] (0.6 g, 0.6 mmol), and benzene(25 cm3) were shaken at room temperature for 2 d. Theyellow-green solution was filtered off and evaporated tosmall bulk. Addition of diethyl ether gave a yellow solid,which was washed with diethyl ether and recrystallisedfrom niethylene chloride-benzene-diethyl ether to giveunchanged [Pt(int)(AsPh,),] (0.11 g, 31y0), m.p.150-154 "C; v(C=O) a t 1 745m, 1 733vw, and 1 711s cm-l.Removal of the solvents from the filtrate and etherwashings and addition of diethyl ether and light petroleumgave a white solid which was washed with petroleum. Thiswas shown to be [Pt(C,F,)(AsPh,),] (0.42 g, 63%) from itsi.r. and lsF n.m.r. spectra; v(C-C) a t 1776 cm-l (lit.,,'?1 775 cm-l).Of [Pt(O,) (PPh,),]. ( a ) With indan-l,2,3-trione. Indan-1,2,3-trione (0.11 g, 0.67 mmol) and [Pt(0,)(PPh3),] (0.5 g1979 2930.67 mmol) in benzene (50 cm3) were stirred for 3 h. Theresulting white suspension was filtered off, washed withbenzene, and recrystallised from methylene chloride-benzene-diethyl ether to give white needles of (6; L =PPh,) (0.3 g, 5 0 0 / ) , m.p.170-172 "C; v(C=O) at 1752sand 1 675s cm-l.As above, ninhydrin (0.06 g, 0.3mmol) and [Pt(O,)(PPh,),] (0.25 g, 0.3 mmol) gave (6;Of [Pt{OC(CF,),*int)(PPh,),l (7). (a) With hexafluoro-propan-2-one. Hexafluoropropan-2-one (ca. 2 cm3) and(7) (0.5 g, 0.48 mmol) in benzene (20 cm3) were shaken a t70 "C, for 2 d. The resulting yellow solution was evaporatedto ca. 5 cm3 and diethyl ether (60 cm3) was added. Theyellow solution was shaken with activated charcoal at roomtemperature, filtered, and the filtrate was evaporated toca, 20 cm3. Light petroleum was added and the solutionwas allowed to stand for 12 h. The yellow solid was filteredoff, washed with petroleum, and recrystallised frommethylene chloride-diethyl ether to give yellow crystals ofunchanged (7) (0.19 g, 38y0), m.p.190-210 "C (decomp.).Addition of methanol to the filtrate and slow evaporationunder reduced pressure gave a white solid which waswashed with methanol. Recrystallisation from methylenechloride-methanol gave white crystals of (8) (0.19 g, 33y0),ni,p. 178-183 "C (decomp.), v(C=O) a t 1732s cm-l.On concentrating the above filtrate another white solidwas obtained. This was washed with diethyl ether and itsi.r. spectrum indicated it t o be a mixture mainly of[Pt(OC(CF,),>(PPh,),] and another unidentified product.Recrystallisation from methylene chloride-diethyl etheryielded a white crystalline solid which was shown to bemainly [Pt{OC(CF,),)(PPh,),] (0.03 g, 7%) by comparisonof its i.r.spectrum with that of an authentic samp1e.lHydrochloric acid(1.2 cm3, 0.100 2 mol dm-3, 0.115 mmol HCl) was added to asolution of (7) (0.12 g, 0.12 mmol) in methylene chloride(20 cm3). The mixture was shaken for 3 d and the whitesolid which formed was filtered off. Addition of diethylether to the filtrate and concentration of the mixture gaveanother crop of the white solid which was shown to be cis-[PtCl,(PPh,),] (0.03 g, 65%) by its m.p. and i.r. spectrum,m.p. 305-310 "C (lit.,24 310-312 "C).The filtrates were evaporated to dryness and addition ofdiethyl ether to the residue gave an off-white solid. Re-crystallisation from chloroform-diethyl ether gave whiteneedles of (6; L = PPh,) (0.04 g, 35y0), m.p. 167-173 "C;v(C=O) a t 1 750s and 1674s cm-l.(c) With hydrogen chloride gas.Passage of hydrogenchloride gas through a solution of (7) (0.1 g, 0.1 mmol) inmethylene chloride (10 cm3) gave cis-[PtCl,(PPh,),] (0.06 g,80y0), m.p. 308-312 "C.(d) With tri;fuoroacetic acid. Excess of trifluoroaceticacid (0.05 g, 0.4 mmol) was added to a solution of (7) (0.2 g,0.2 mmol) in methylene chloride (10 cm3). Diethyl etherwas added to the colourless solution and evaporation underreduced pressure gave white crystals of [Pt(O,CCF,),-(PPh,),] (0.13 g, 70y0), m.p. 220-223 "C (lit.,,, 230-235 "C).Of [Pt{ (int),)(PPh,),] (2). (a) With hexafluorobut-2-yne.Hexafluorobut-2-yne (ca. 1.5 cm3) and (2) (0.44 g 0.42mmol) in benzene (25 cm3) were shaken at 60 "C for 4 h.The yellow-green solution was evaporated to dryness.The residue was dissolved in diethyl ether and the solutionwas filtered.Addition of methanol and evaporation tosmall bulk gave a white solid which was recrystallised from(b) With ninhydrin.L = PPh,) (0.2 g, 67%).(b) With aqueous hydrochloric acid.methylene chloride-methanol to give white crystals of[Pt(C,F,)(PPh,),] (0.26 g, 70y0), m.p. 213 "C (lit.,26 215-216 "C).(b) With hexafluoropropan-2-one. Hexafluoropropan-2-one (ca. 1.5 cm3) and (2) (0.56 g, 0.54 mmol) in benzene(30 cm3) were shaken at room temperature for 3 d. Thered crystals which formed were filtered from the blue-greensolution and were identified as indan-1,2,3-trione (0.04 g,47y0), m.p. 240-244 "C (lit.,14 241-243 "C).The filtrate was evaporated to ca.10 cm3 and addition ofdiethyl ether gave a pale yellow solid contaminated withred crystals of indan-1,2,3-trione. The mixture wasfiltered off, washed with diethyl ether, and recrystallisedfrom methylene chloride-diethyl ether. The yellow crystals(0.24 g, 43%) were shown to be identical to (7), m.p. 190-210 "C (decomp.); v(C=O) a t 1 760vw, 1 733m, and1 705s cm-l.The filtrate and diethyl ether washings were evaporatedto ca. 2 cm3 and addition of diethyl ether gave a pale yellowsolid which was filtered off and washed with diethyl ether.Recrystallisation from methylene chloride-diethyl ethergave white crystals having a stoicheiometry correspondingto a 1 : 1 adduct between (4) and hexafluoropropan-2-one(0.06 g, llx), m.p. 270-290 "C (decomp.) (Found: C,54.2; H, 3.2; F, 10.0.C48H34F,04P,Pt requires C, 55.2;H, 3.3; F, 10.9%); v(C=O) a t 1728s cm-l. Infraredspectrum: 1 728s, 1 608w, 1 600vw, 1 587vw, 1 572vw,1483m, 1439s, 1341vw, 1312m, 1 292m, 1278s, 1223s,1212s, 1 191vw, 1 180m, 1 159m, 1 150m, 1 121s, 1 104111,1096m, 1081m, 1042s, 1 009m, 972s, 943m, 902m, 879m,804vw, 778m, 763m, 752m, 727s, 714m, 700s, 623w, 562m,549m, 538m, 526m, 518m, and 504m cm-l.The solvents from the filtrate and diethyl ether washingswere evaporated to dryness and diethyl ether was addedto the residue. A white solid slowly precipitated and twoadditional crops were obtained in this way. The whiteprecipitates were recrystallised from methylene chloride-methanol to give white crystals of (8) (0.22 g, 34%) identifiedby its i.r.spectrum and m.p. 174-184 "C (decomp.) (gasevolved) ; v(C=O) a t 1 731s cm-l.X-Ray Crystallographic Study.-Recrystallisation from avariety of solvents did not yield good-quality crystals of theadduct (2). However, an irregular bright yellow crystal ofdimensions ca. 0.057 x 0.027 x 0.025 cm was isolated frombenzene-diethyl ether solution and used for the measure-ment of cell constants and intensities. Unit-cell dimensionswere obtained from precession photographs using Mo-K,radiation.Crystal data. C,4H&,P,Pt, M = 1039.9, Monoclinic,U = 9 438 Hi3, D, = 1.46 g ~ m - ~ , 2 = 8, ~(Mo-K,) =32.4 cm-l, space group Cc.Intensities were measured in 14 layers, h0l through h13l,on a Stoe Weissenberg diffractometer using monochromaticMo-K, radiation ( A = 0.710 7 A) and an w-scan technique.The 2 382 reflections with significant intensity [ I > 2441and 0.1 < (sin0)h < 0.7 A-1 were corrected for Lorentz,polarisation, and absorption 27 effects.Scattering factors for the atoms were taken from ref.28.The three-dimemional Patterson function indicated thatboth unique platinum atoms had y co-ordinates of ca.with the result that only 314 reflections with significantintensity break the pseudo-F-centring thus introduced.Nevertheless, the remaining non-hydrogen atoms could bedistinguished and the two molecules resolved usingu = 22.08(2), b = 14.47(1), c = 30.72(2) A, p = 95.1(5)"294 J.C.S. DaltonTABLE 3Final atomic co-ordinates * with estimated standard deviations in parenthesesMolecule 1 Molecule 2A r 7 r J.xla0.281 3(1)0.256 l(7)0.213 3(6)0.355(3)0.423( 3)0.303(3)0.350 (3)0.408 (3)0.339 (3)0.36 1 (2)0.478(2)0.256 (2)0.303(2)0.441(2)0.291(2)0.4100.3470.4420.400Y lb0.256 7(3)0.138 l(11)0.366 l(11)0.208(5)0.166 (6)0.151 (6)0.32 7 (6)0.36 1 (6)0.348 (6)0.184(3)0.162(3)0.152(3)0.344 (3)0.367(3)0.309(3)0.1420.1350.3940.378Z l C0.260 8(1)0.306 5(4)0.274 4(4)0.1 95 ( 2)0.183(2)0.163(2)0.192( 2)0.146(2)0.244(1)0.204( 1 )0.173( 1)0.238(1)0.118( 1)0.1370.1260.1640.1270.201 (2)0.212(1)%la0.00.064 l(9)0.032 4(8)- 0.072(3)-0.135(3)-0.051(3)- 0.073(3)-0.133(3)-0.027(3)- 0.030(2)- 0.143(2)- 0.003( 2)- 0.065(2)- 0.177( 2)- 0.148- 0.101-0.115-0.0510.02 1 (2)Y lb Z l C0.243 O(3) 0.00.138 6(0.340 6(0.199 (6)0.145(6)0.175( 6)0.296(5)0.333 (6)0.346 (6)0.151 (3)0.100( 3)0.155( 3)0.317(3)0.324(3)0.38 l(3)0.1140.1320.3760.3756) -0.15 4(4) -0.045 t0.069(50.060(:0.125(50.066(:0.080( f0.093(20.044( 10.024(10.138( 10.023(10.064( 10.085(10.1050.1390.1260.133* Co-ordinates for the remaining phenyl carbon atoms have been deposited with the structure-factor table.successive Fourier syntheses.Hydrogen atoms were notincluded in the structure-factor calculations and in view ofthe limited and poor-quality data the phenyl groups weregiven a fixed geometry (viz.planar with C-C 1.395 %, andC-C-C 120") and only the position and orientation of thegroups was varied. Carbon and oxygen atoms were giventemperature factors B of 5.0 and 3.0 A2 respectively. Theselight-atom temperature factors were not refined.Limitations on computer storage necessitated the refine-ment of the parameters for the two independent moleculesin alternate least-squares cycles. The above mentionedpseudo-centring together with the use of a block-diagonalapproximation probably means that the e.s.cl.s from theleast-squares refinement are underestimated. Refinementconverged with R 0.078 for the 2 382 reflections. Thefunction mininiised was XwA2 where the weighting schemegiven by w = (656.0 - 8.11F01 + 0.041F,12)-1 was intro-duced in order that wA2 be approximately independent ofIF,].The maximum shift in the final cycle was 0.30.Final atomic parameters are listed in Table 3. A list ofobserved and calculated structure factors and thermalparameters is available as Supplementary Publication No.SUP 22371 (16 pp.).*We thank Johnson, Matthey Ltd., for the generous loanof platinum metal salts, the S.R.C. for support, and theUniversity of Leicester Computing Laboratory for the use ofits facilities.[8/841 Received, 5th May, 19781REFERENCESJ . Chem. SOC. ( A ) , 1968, 167.1 B. Clarke, M. Green, R. B. L. Osborn, and F. G. A. Stone,2 A. De Cian and R. Weiss, Acta Cryst., 1972, B28, 3273.* For details see Notices to Authors No. 7, J.C.S. Dalton, 1977,Index issue.A. M. Brodie, B. F. G. Johnson, P. L. Josty, and J. Lewis,R. B. King and A. Fronzaglia, Inorg. Chem., 1966, 5, 1837.R. E. Moriarty, R. D. Ernst, and R. Bau, J.C.S. Chem. Comm,,13 J . Burgess, J. G. Chambers, D. A. Clarke, and R. D. W.M. Green, N. R. Mayne, R. B. L. Osborn, and F. G. A. Stone,J . A. Evans, G. F. Everitt, R. D. W. Kemmitt, and D. R.lo J . Browning, H. D. Empsall, M. Green, and F. G. A. Stone,l1 M. P. Cava and R. Pohlke, J . Org. Chem., 1962, 27, 1564.l2 A. Schonberg. and E. Singer, Chem. Ber., 1971, 104, 160.l3 R. D. W. Kemmitt and R. D. Moore, J . Chem. SOC. ( A ) , 1971,l4 P. J . Hayward, D. M. Blake, G. Wilkinson, and C. J . Nyman,l5 P. J. Hayward and C. J . Nyman, J . Amer. Chem. SOC., 1971,J.C.S. Dalton, 1972, 2031.1972, 1242.Kemmitt, J.C.S. Dalton, 1977, 1906.J . Chem. SOC. ( A ) , 1969, 1879.Russell, J.C.S. Chem. Comm.. 1973, 158.J.C.S. Dalton, 1973, 381.* M. B. Rubin, Chem. Rev., 1975, 75, 177.2472.J. Amer. Chem. SOC. 1970, 92, 5873.93, 617.P. J. Hayward, S. J . Saftich, andC. J. Nyman, Inorg. Chem.,1971, 10. 1311.l7 T. A. Stephenson and G. Wilkinson, J . Inorg. Nuclear Chem.,l8 W. 0. Teeters and R. L. Shriner, J . Amer. Chem. SOC., 1933,l9 L. Malatesta and C. Cariello, J . Chem. SOC., 1958, 2323.2o J. Chatt, B. L. Shaw, and A. A. William , J . Chem. SOC.,21 A. D. Allen and C. D. Cook, Canad. J . Chem., 1964, 4, 1063.22 C. J . Nyman, C. E. Wymore, and G. Wilkinson, J . Chem.23 J. P. Collman and J. W. Kang, J . Amer. Chem. SOC., 1967,89,24 J. C. Bailar and H. Itatani, Inorg. Chem., 1965, 4, 1618.25 Y . S. Sohn and A. L. Balch, J . Amer. Chem. Soc., 1971, 93,25 J. Boston, S. 0. Grim, and G. Wilkinson, J . Chem. SOC..27 J . de Meulenaer and H. Tompa, Acta Cryst., 1965, 19, 114;28 D. T. Cromer and J. T. Waber, Acta Cryst., 1965, 18, 104.1967, 29, 2122.55, 3026.1962, 3269.SOC. ( A ) , 1968, 561.844.1290.1963, 3469.N. W. Alcock, ibid., 1969, A25, 518

ISSN:1477-9226    

DOI:10.1039/DT9790000287

出版商:RSC    

年代:1979

数据来源: RSC