摘要:

J. CHEM. soc. DALTON TRANS. 1988 1185Organo-Platinum-Iron Complexes derived from Allenes. Crystal Structures of(p-C(=CH,)CH,}Pt( PPh,)], and [(oC),Fe(p-dppm){~f-(CH,)(CMe,)CPt(PPh~)}] tr (OC), Fe(P-dPPm){P-C(O) c H,C(=CH,))Pt( pph,)l r (OC), F d p-dppm) -Xavier L. R. Fontaine, Grant B. Jacobsen, Bernard L. Shaw," and Mark Thornton-PettSchool o f Chemistry, University of Leeds, Leeds LS2 9JTTreatment of [ (OC),Fe(p-dppm) (p-CO) Pt( PPh,)] ( I ) (dppm = Ph,PCH,PPh,) with allene at 20 "Cin dichloromethane gave [ (OC),Fe(p-dppm){p-C(O)CH,C(=CH,)}Pt( PPh,)] (3) in moderate yield.Its structure was established by X-ray crystallography; the crystals are orthorhombic, space groupPbca with a = 2 481.5(3), b = 1 906.2(2), c = 1 838.7(3) pm, and Z = 8; R 0.031 5 for 4 401observed reflections.The allene ligand has inserted into the Pt-C bond of the bridging carbonyl of(1 ) to give a dimetallacyclopentanone ring with an exocyclic methylene group. Treatment ofcomplex (1 ) with allene at 80 "C gave [(OC),Fe(p--dppm){p-C(=CH,)CH,}Pt( PPh,)] (5) inmoderate yield. The structure of (5) was also established by X-ray crystallography; the crystals aremonoclinic, space group P2,/n, with a = 1 195.1 (2), b = 2 258.5(3), c = 1 673.9(4) pm,B = 108.1 5(2)", and Z = 4; R 0.0286 for 4 835 observed reflections. The allene ligand is bridgingthe Fe-Pt bond t o give a dimetallacyclobutane ring with an exocyclic methylene group. Whencomplex (3) or (5) was heated at 80 "C the complex [(0C),Fe(p-dppm){q4-(CH,),CPt(PPh3)}] (6)was formed in high yield.Analogues of (6) were prepared by treatment of (1) with the substitutedallenes PhCH=C=CH, and Me,C=C=CH,, viz. [(OC),Fe(p-dppm){q4-(CH,)(CHPh)CPt(PPh,)}J ( 7 )and [(OC),Fe(p-dppm){q4-(CH,)(CMe,)CPt(PPh,)}] (8). The structure of (8) was establishedby X-ray crystallography; the crystals are monoclinic, space group P2,/c, with a = 1 098.4(3),b = 1 889.8(6), c = 2 21 6.3(5) pm, p = 103.52(2)", and Z = 4; R 0.031 1 for 5 080 observedreflections. It is most informatively viewed as a phosphine-substituted platinatrimethylenemethanecomplex in which the (CH,) (CMe,)CPt(PPh,) (dppm-P) moiety is q4-co-ordinated to Fe.Protonation of (5) with H BF,-OEt, gave the p-propenyl cation [ (OC),Fe(p-dppm){p-C( Me)=CH,}-Pt( PPh,)] [ BF,] exclusively.Some similar chemistry with the diphosphine (Ph,P),C=CH, is alsodescribed.In a recent publication' we described the preparation ofthe electron- rich hetero bime tallic complex [ (OC) Fe(p-dppm)-(p-CO)Pt(PPh,)] (1) (dppm = Ph2PCH,PPh,) and its sub-sequent reactions with aikynes to give complexes containingdimetallacyclopentenone rings. We expected that (1) might alsobe reactive towards allenes, however, the nature of the productswas difficult to predict because of the possibility of isomeris-ation of co-ordinated allene to co-ordinated alkyne. Severalbimetallic complexes containing co-ordinated allenes havebeen prepared previously and structurally characterised: [Mo,-(p-CH2=C=CH z)],3 and [Fez( q '-C,H 4,( CO),( p-CHz=C=CH,)14 were all shown to have 'V-shaped' allene ligandssymmetrically bridging the two metal centres and allene wasconsidered to form one olefin-metal bond to each metal.Theallene complex [Rh,(acac)(CO),(p-CHz=CSH2)] (acac =acetylacetonate) was also shown to have a bridging alleneligand but in this case there was no metal-metal bond.In this paper we describe the reactions of the iron-platinumcomplex (1) and its analogue with Ph,PC(=CH,)PPh, (vdpp)(2) with allenes to give new organoplatinum-iron complexes.(~5-C5HS)2(C0)4(~L-CHZ=C=CH,)1,2 [Mn2(qs-CSH5)Z(C0)3-t ~-Bis(diphenylphosphino)methane-2,2,2-tricarbonyl-~-[ 1'-oxobut-3'-ene- 1 ',3'-diyl-C' '(Fe)C3'(Pt)]-l-triphenylphosphineplatinumiron-(Pt-Fo), ~-b1s(diphenylphosphino)methane-2,2,2-tricarbonyl-~-[~~rop-2'-ene- 1 ',2'-diyl-C "( Pt)C2'(Fe)]- l-triphenylphosphineplatinumiron-(Pf-Fc).and ~-bis(diphenylphosphino)methane-2,2-dicarbo~yl-~-[3'-methylbut-2'-en- 1 ,2'-diyl-C"3'(Fe)C2'(Fe,Pt)]- 1 -triphenyl-phosphineplatinumiron( Pt-Fe).Suppkementur), tkutu uvuiluble: see Instructions for Authors, J. ('hem.Soc.. Dulton Truns., 1988, Issue 1, pp. xvii-xx.Aspects of this work have appeared as a preliminary com-munication.6Results and DiscussionTreatment of a dichloromethane solution of [(OC),Fe-(p-dppm)(p-CO)Pt(PPh3)] (1) with allene at ca. 20 "C gave,after several days, the complex [(OC),Fe(p-dppm){ p-C(0)-CH,C(=CH,))Pt(PPh,)] (3) in 35% isolated yield. The vdppanalogue [(0C),Fe(p-vdpp){p-C(0)CH2C(=CHz))Pt(PPh3)](4) was similarly prepared from [(OC),Fe(p-vdpp)(p-CO)Pt(PPh,)] (2) in 27% yield.Complexes (3) and (4) werecharacterised by elemental analysis and i.r. spectroscopy(Table I), and by 31P-{ 'H} (Table 2) and 'H (Table 3) n.m.r.spectroscopy; preparative details are given in the Experimentalsection. The ,lP-( 'H} n.m.r. spectra of (3) and (4) were similarand each consisted of three resonances, a low-field resonancewith satellites due to a small coupling to 195Pt [J(PtP) 60-66Hz] assigned to the phosphorus atom bonded to iron and twohigher-field resonances also with 195Pt satellites [J(PtP) ca.3 000 and ca. 1900 Hz] assigned to the phosphorus atomsbonded to platinum. The large values of J(P,P,) across thedppm or vdpp ligands of 102 and 162 Hz respectively madepossible the individual assignments of each of the phosphorusatoms on platinum, i.e.PA and P,. The 'H n.m.r. spectra bothshowed similar resonances which were assigned to the protonsof the co-ordinated allene ligands, uiz. two mutually coupledresonances, each of relative intensity one, at ca. 5.2 and ca. 4.3p.p.m. [J(HH) 1.5 Hz] assigned to the vinylic protons (CSH,),and a resonance at ca. 3.6 p.p.m., of relative intensity two,assigned to the methylene protons on the carbon atom adjacentto the C=O. The i.r. spectra were similar in the carbonyl regio1186(31( 4 )PnP = dppmPnP = vdppJ. CHEM. SOC. DALTON TRANS.P P (1) P -P = dppm(OCI3Fe-Pt(PPh3) (2) PnP = vdppnI 1'C'0n n-P = dppm(OC)3Fr-\t(PPh3) 9 7 ( 5 ) PHC - CHZ 1) CHZi ' iI Iofic\c,c*c H2(OC),Fe- Pt(PPh3)H2( 1 1 1 1P PIH1988+B F i( 7 ) P -P = dppm; R1 = H I R2 = Ph (9) PnP = dppm( 8 )Scheme.(i) CH,=C=CH,, CH,Cl,, 20 "C; (ii) CH,=C=CH,, benzene, 80 "C; (iii) benzene, 80 "C; (iv) PhCH=C=CH,, benzene, 80 "C, orMe,C=C=CH,, CH,CI,, 40 "C; ( I J ) HBF,*OEt,Table 1. Infra-red" and analyticalb dataAnalyses (%)r 1Complex v( C=O)/cm-' C H(3).0.5CH2C1, 1986~, 1918~, 1 8 4 4 ~ , 1 622s 55.45 3.9(55.25) (3.8)(4) 1985s, 1 920s, 1 885s, 1616s 57.6 4.05(57.7) (3.9)(5).C,H, 1972s, 1912s, 1884s 59.7 4.15(60.05) (4.3)(6) 1948s, 1 888s 58.1 4.3(58.0) (4.15)(60.65) (4.25)(58.8) (4.45)Calculated values in(7) 1 950s, 1 890s 60.0 4.2(8) 1940s, 1 885s 58.5 4.4, As solutions in dichloromethane; s = strong.parentheses.and both showed three bands assigned to terminal carbonylligands and a very low-energy band at ca. 1 620 cm-',suggesting the presence of a ketonic type carbonyl.These datadid not unambiguously define the structures of complexes (3)or (4) and so an X-ray diffraction study was undertaken on acrystal of (3).Cr-vstal Structure of [(OC),Fe(p-dppm){p-C(O)CH,C-(=CH,)}Pt(PPh,)] (3).-The allene complex (3) was crystallisedfrom dichloromethane-diethyl ether (1 : 3) solution. Thestructure is shown in Figure 1 and selected intramoleculardistances and angles are in Table 4. The iron and platinummoieties are linked by a single dppm bridge to give a five-membered FePCPPt ring. The Fe-Pt distance of 267.3(4) pmindicates a metal-metal bond and is close to those found inthe related complexes [( OC) , Fe( p-dppm)(p-CO)Pt( PPh ,)I,257.9(4) pm, and [(OC),Fe(p-dppm){ p-C(O)C,H,}Pt(PPh,)],259.7(4) pm.1*6 The allene ligand has inserted into the bridgingcarbonyl Pt-C bond of (1) to give a dimetallacyclopentanonering containing an exocyclic methylene group.The organicligand is therefore a simple one-electron donor to each metalatom. The Fe-C(4) distance, 201.1(10) pm, and Pt-C(6)distance, 206.7(9) pm, are similar. The C(6)-C(7) distance,134.8( 12) pm, is close to that found for the C=C double bondin the bridging vinylidene complex [Ru,(q 5-C,H,),(C0)2-(p-CO)(p-C=CH,)], 132.6(11) ~ m , ~ and IS typical of theseparation for an uncomplexed C=C double bond such as inethylene, 133.7(3) pm.8 The C(4)-C(5) and C(5)-C(6) distances,150.3( 12) and 146.4( 1 1) pm, respectively, are typical of sp2-sp3hybridised C-C bonds while the C(4)-0(4) distance of 122.9(9)pm is similar to that of the analogous bond in the dimetalla-cyclopentenone [(OC),Fe(p-dppm){p-C(O)C,H,)Pt(PPh,)l,121.3(10) pm.' The geometry of the metallacyclic ring in (3)shows that the Pt, Fe, C(4), and C(5) atoms are approximatelyin a plane, with C(6), bearing the exocyclic methylene group, outof that plane, i.e.the five-membered ring is in an envelope con-formation. The structure of (3) makes an interesting comparisonwith that of the dimetallacyclopentenone complex [(OC),Fe-(p-dppm){ p-C(O)C,H,}Pt(PPh,)] formed from acetylene.' Inthis complex the co-ordinated acetylene is able to make a n:interaction with the iron centre which has lost a terminalcarbonyl ligand.Although related, the complexes derived fromacetylenes and allenes are structurally quite different.1187 J. CHEM. SOC. DALTON TRANS. 1988Table 2. 3 1 P-{ 'H) N.m.r. data (6)Complex(3) 56.2 [dd, PA, J(PAPB) 102, J(PAPc) 10, J(PtPA) 66126.0 [dd, Pc, J(PAPc) 10, J(PBP,) 9, J(PtPc) 3 210117.9 [dd, P B , J(PAPB) 102, J(P,Pc) 9, J(PtPB) 1 880164.5 [dd, PA, J(PAPB) 162, J(PAPc) 10, J(PtPA) 60127.3 [dd, PB, J(PAPB) 162, J(PBPc) 8, J(PtPB) 1 928126.3 [dd, Pc, J(PAPc) 10, J(PBPc) 8, J(PtPc) 3 060176.7 [d, PA, J(PAPB) 127, J(PtP,) 86130.4 [d, PB, J(PAPB) 127, J(PtPB) 2 0761(4)( 5 )28.2 [s, P,, J(PtPc) 3 3841(6) 49.1 [dd, P A , J(PAPB) 57, J(PAPc) 37, J(PtPA) 209146.6 [dd, Pc, J(PAP,) 37, J(PBPc) 5, J(PtPc) 2 96413.2 [dd, Pg, J(PAP,) 57, J(P,Pc) 5, J(PtPB) 2 600147.8 [dd, PA, J(PAP,) 55, J(PAPc) 35, J(PtPA) 220337.7 [d, Pc, J(PAPc) 35, J(PtPc) 3 02012.2 [d, PB, J(PAPB) 55, J(PtPB) 2 6051(7)(8) 46.6 [dd, PA, J(PAPB) 58, J(PAPc) 35, J(PtPA) 225136.2 [d, P,, J(PAPc) 35, J(PtPc) 2 99010.9 [d, PB, J(PAPB) 58, J(PtPB) 2 6651Recorded at 162 MHz in CH,CI, solution, at 20 "C.Positive shifts tohigh frequency of external 85% H3P0,. Coupling constants in Hz. PAand P, refer to the dppm or vdpp phosphorus atoms bonded to ironand platinum, respectively, P, to the triphenylphosphine phosphorusatom. The multiplicity, i.e. d or dd, refers to the P-P coupling.Figure 1.Molecular structure of [(OC),Fe(p-dppm){ p-C(O)CH,C-(=CH,)} Pt( PPh,)] (3) showing the principal atomic numbering3 1 P-( ' H ) N.m.r. studies of the reaction between (1) and alleneindicated an intermediate complex in the formation of (3). Thisintermediate appeared to contain a monodentate dppm ligandco-ordinated to iron, similar to that observed in the reactionbetween (1) and alkynes.' Presumably, the allene and alkynereactions proceed by similar mechanisms, possibly involving anintermediate with the organic ligand q'-bonded to platinum.When (1) was heated in benzene to 80 "C with allene bubblingthrough the solution the complex [(OC),Fe(p-dppm){p-C-(=CH,)CH,)Pt(PPh,)] (5) was obtained in 57% yield. Attemptsto prepare the vdpp analogue from (2) failed, only decom-position products being formed.Complex (5) was characterisedby elemental analysis, and i.r., ,lP-{ 'H} and 'H n.m.r. spectro-scopy (see Tables for details). The ,lP-{ 'H} n.m.r. spectrum wassimilar to those of complexes (1) and (3), suggesting that theTable 3. Selected 'H n.m.r. dataQ (6)Complex(3) 5.23 [ddd, 1 H, C=CH,, J(PBH) 16, J(P,H) 4, J(HH) 1.5,J(PtH) 7214.33 [dd, 1 H, C=CH,, J(PBH) 9, J(HH) 1.5, J(PtH) 3713.68 [d, 2 H, C(O)CH,, J(PBH) 6, J(PtH) 4113.55 [dd, 2 H, PCH,P, J(PAH) 10, J(PBH) 10, J(PtH) 261(4) 5.43 [dd, 1 H, P,C=CH,, J(PH) 27 and 1415.42 [dd, 1 H, P,C=CH,, J(PH) 25 and 1515.21 [ddd, 1 H, C=CH,, J(PH) 20 and 4, J(HH) 1.5,4.31 [dd, 1 H, C=CH,, J(PH) 9, J(HH) 1.5, J(PtH) 3613.59 [d, 2 H, CH,, J(PH) 6, J(PtH) 4215.1 1 [s, 1 H, C=CH,]3.33 [m, 2 H, PCH,P, J(PtH) 3011.93 [br, 2 H, PtCH,, J(PtH) 6415.12 CAB, 1 H, PCH,P, J(HH) 15, J(PtH) 7013.97 CAB, 1 H, PCH,P, J(HH) 1513.71 [s, 1 H, CH,, J(PtH) 5313.02 [d, 1 H, CH,, J(PH) 7, J(PtH) 12712.90 [d, 1 H, CH,, J(PH) 6, J(PtH) 11614.72 (br, 2 H, PCH,P)3.95 [s, 2 H, CH,, J(PtH) 5513.30 [d, 2 H, CH,, J(PH) 7, J(PtH) 12315.95 [d, 1 H, CHPh, J(PH) 5815.19 CAB, 1 H, PCH2P, J(HH) 15, J(PtH) 6514.00 CAB, 1 H, PCH,P, J(HH) 1513.65 [d, 1 H, CH,, J(PH), 7, J(PtH) 12113.38 [br, 1 H, CH,, J(PtH) 5835.22 CAB, 1 H, PCH,P, J(HH) 15, J(PtH) 6613.93 CAB, 1 H, PCH2P, J(HH) 15, J(PtH) 51J(PtH) 741(5) 5.52 [d, 1 H, W H , , J(PAH) 41(6)*3.25 [ s , 1 H, CH,, J(PtH) 531(6)'(7)(8)3.09 [dd, 1 H, CH,, J(PBH), 7, J(PcH) 1, J(PtH) 5813.00 [dd, 1 H, CH,, J(PAH) 9, J(PBH) 5, J(PtH) 11811.85 (s, 3 H, CH3)1.42 (s, 3 H, CH,)Recorded in CDCI, solution at 20 "C and 400 MHz, unless statedotherwise.Chemical shifts (6) in p.p.m. (i-0.01 p.p.m.) relative toSiMe,, coupling constants (J) in Hz (k0.3 Hz); 31P-{1H} couplingconstants are quoted only when resolved and are specifically assigned(i.e. to PA, P,, or P,) only when confirmed by double-irradiationexperiments, PA and P, referring to the dppm or vdpp phosphorusatoms bonded to iron and platinum, respectively, P, to the triphenyl-phosphine phosphorus atom. Recorded at - 20 "C. ' Recorded inC,D,CD, solution at 100 "C.metal-phosphine backbone was unchanged. The H n.m.r.spectrum showed resonances assigned to a co-ordinated alleneligand, uiz.two resonances, each of relative intensity one, at 5.52and 5.11 p.p.m. assigned to the vinylic protons (C=CH,) and aresonance, of relative area two, at 3.33 p.p.m. assigned to themethylene (CH,) protons. The i.r. spectrum showed three bandsassigned to terminal carbonyl ligands. These data did notunambiguously define a structure for (5) and so a single-crystalX-ray diffraction study was undertaken.Crystal Structure of [(OC),Fe(p-dpprn){p-C(=CH,)CH,)-Pt(PPh,)] @).-The allene complex ( 5 ) was crystallised fromchlorobenzene-methylcyclohexane (1 : 3) solution. The structureis shown in Figure 2 and selected intramolecular distances andangles are in Table 5. The iron and platinum moieties are linkedby a single dppm bridge to give a five-membered FePCPPt ringwith an Fe-Pt distance of 263.4(4) pm. This indicates a metal-metal bond and is similar to that found in (3).The allene ligandhas displaced the bridging carbonyl in (1) and is now bridgingthe Fe-Pt bond to give a dimetallacyclobutane ring containingan exocyclic methylene group. The metallacyclic ring is almostplanar. The Fe-C(5) distance of 208.8(7) pm and the Pt-C(4)1188 J. CHEM. SOC. DALTON TRANS. 1988C(224)Table 4. Selected distances (pm) and angles (") between interatomicvectors for [(OC),Fe(p-dppm){ p-C(0)CH,C(=CH2))Pt(PPh3)] (3)Fe-PtP( 3)-PtC( 3)-PtP( 2)-FeC(2)-FeC (4)-FeC( 13)-P(2)0(2)-C(2)0(4)-C(4)C(6)-C(5)P( 1)-Pt-FeP(3)-Pt-P( 1)P( 2)-Fe-PtC( 1)-Fe-P(2)C( 2)-Fe-P( 2)C(3)-Fe-PtC(3)-Fe-C( 1)C(4)-Fe-PtC(4)-Fe-C( 1)C(4)-Fe-C(3)C( 13)-P(2)-PtFe-C( 1)-PtO( 1)-C( 1)-FeFe-C( 3 )- P t0(3)-C(3)-FeC(5)-C(4)-FeC(6)-Pt-P( 1)C( 6)-C( 5)-C(4)C(7)-C(6)-Pt267.3(4)228.9(4)274.7( 10)224.4(4)174.4( 10)183.4(8)116.7(9)122.9(9)146.4(11)20 1.1 (10)92.61 0 1.9( 2)163.2(2)96.1(2)90.8( 3)87.7(3)73.4(3)143.3(3)90.2(3)9 3.2(4)82.4(4)71.3(3)174.1(6)68.9(3)177.0(6)1 18.6(6)11 1.7(7)121.4(7)111.7(3)P( 1)-PtC(1)-PtC(6)-PtC( 1)-FeC(3)-FeC( 13)-P( 1)O( 1 )-C( 1)0(3)-C(3)C(5)-C(4)C(7)-C(6)P(3)-Pt-FeC(6)-Pt-FeC( 1 )-Fe-PtC( 2)-Fe-PtC(2)-Fe-C( 1)C( 3)-Fe-P(2)C(3)-Fe-C(2)C(4)-Fe-P( 2)C(4)-Fe-C( 2)C( 13)-P( 1)-PtP(2)-C( 13)-P( 1)O( 1 )-C( 1)-Pt0(3)-C(3)-PtC( 5)-C(4)-0(4)C( 5)-C( 6 t P tC(7)-C(6)-C(5)C(6)-Pt-P( 3)0(2)-C(2)-Fe0(4)-C(4)-Fe232.4(4)265.5(9)206.7( 9)I 75.8( 10)175.2(10)184.5(8)1 18.2(9)150.3( 12)134.8( 12)1 17.4(9)160.481.0(3)88.4(3)70.2(3)176.2(2)109.5(4)1 06.5(4)173.3(2)86.0(4)1 1 1.0(3)110.3(4)113.5(6)178.3(7)112.3(6)1 24.3( 7)117.0(8)119.1(6)118.3(8)97.4(3)Table 5.Selected distances (pm) and angles (") between interatomicvectors for [(OC),Fe(p-dppm){ p-C(=CH,)CH,)Pt(PPh3)] (5)Fe-PtP(3)-PtC(2)-PtP( 2)-FeC(2)-FeC(S)-Fe0(2tC(2)C(5)-C(4)C( 13)-P(2)P( 1)-Pt-FeP(3)-Pt-P( 1)C(4)-Pt-P( 1)P(2)-Fe-PtC( 1)-Fe-P(2)C( 2)-Fe-P(2)C( 3)-Fe-PtC(5)-Fe-PtC( 5)-Fe-C( 1)C(5)-Fe-C(3)C( 13)-P(2)-Fe0(2)-C(2)-PtC( 5)-C(4)-PtC(6)-C(5)-Fe263.4(4)23 2.8( 3)273.7( 9)224.3( 3)180.6(8)208.8( 7)184.8(6)145.0( 1 1)1 15.4(9)92.6104.1166.1(2)100.993.7(3)92.4(3)164.0(2)72.9(3)78.2(3)92.0(3)110.4(3)177.2(5)105.1(6)129.2(7)P(3)-Pt-FeC(4)-Pt-FeC(4)-Pt-P(3)C( 1 )-Fe-PtC( 2)-Fe-PtC(2)-Fe-C( 1)C(3)-Fe-C(2)C(5)-Fe-P(2)C( 5)-Fe-C(2)C( 13)-P( 1)-PtO(1)-C( 1)-FeO( 3)-C( 3)-FeC(4)-C(5)-FeC(6)-C(5FC(4)232.6(3)270.8(9)209.3( 8)182.0(8)1 78.5( 8)187.0(8)118.5(9)135.0(9)1 15.4(9)162.973.7(3)73.5(3)89.7( 3)72.3(3)145.8(3)102.5 (4)170.9(2)92.ii3j113.5(2)178.9(4)176.9(6)106.8( 5)123.9(7)distance of 209.3(8) pm are nearly the same.These distances,along with the pairs of almost equal angles, Fe-Pt-C(4) 73.7(3)and Pt-Fe-C(5) 72.9(3)", and Pt-C(4)-C(5) 105.1(6) andFe-C(5)-C(4) 106.8(5)", illustrate the very symmetrial bridging ofthe allene ligand across the Fe-Pt bond. The C(5)-C(6) distanceof 135.0(9) pm is similar to that found for the analogous moietyin (3), 134.8(12) pm. The C(4)-C(5) distance of 145.0(11) pm istypical of an sp2-sp3 hybridised C-C bond, again similar to thatfound in (3), 146.4( 11) pm. Structure ( 5 ) can be viewed as aC(114) c(115fl . 2 3 3 4 )C(313) u C(123)C(314)Figure 2. Molecular structure of [(OC>,Fe(p-dppm){p-C(=CH,)CH,)-Pt(PPh,)] ( 5 ) showing the principal atomic numberingsubstituted p-ethylene complex. Such a complex has beenproposed as a possible intermediate in the borane reduction ofthe p-ketene complex [Ru,(q s-C,Me,)2(CO),(p-CO){p-C(0)-CH,)] to give, ultimately, p-ethylidene and terminal ethylenecomplexes.Presumably, the exocyclic double bond in (5)stabilises the p-olefin type structure and makes suchrearrangements less favourable.It is interesting to compare the allene bonding in complex (5)with that found in (3). In (3) the allene inserts into the Pt-Cbond of (1) under mild conditions to give a structure with theexocyclic methylene group of the organic ligand adjacent toplatinum. In (5) however, the exocyclic methylene group isfound to be adjacent to iron. These results suggest differentmechanisms for the formation of (3) and (5) from (1). Weattempted the conversion (3) + (5) by heating a benzenesolution of (3), however no (5) was observed and a near-quantitative transformation occurred to give the new com-pound [(OC),Fe(p-dppm)(q4-(CH,),CPt(PPh3))] (6).Thelatter was also formed, again quantitatively, by heating (5)in benzene. Analogues of (6) with 3-phenyl- 1,2-propadieneand 3-methyl-172-butadiene, uiz. [(OC),Fe(p-dppm)(q4-(CH,)-(CHPh)CPt(PPh,))] (7) and [(OC),Fe(p-dppm)(q4-(CH2)-(CMe,)CPt(PPh,))] (8), were also prepared by treating (1)directly with the appropriate allene (see Experimental sectionfor details). Complexes (6)-(8) were characterised by elementalanalysis, and i.r., 31P-('H) and 'H n.m.r. spectroscopy (seeTables for details). The 31P-(1H) n.m.r. were very similarsuggesting analogous structures for these complexes.Addition-ally, they were of the same form as those of complexes (l), (3),and (5) implying a retention of the metal-phosphine back-bone. A two-dimensional COSY 3 1 P-('H} n.m.r. spectrumand J(PtP,) = + 2 964 Hz (one-bond Pt-P couplings arealways positive). These results are similar to those previouslyfound for (l).' Additionally, the study established that J(PAPB)was of a different sign to J(P,P,) and J(P,P,). The i.r. spectra ofcomplexes (6)-(8) all showed two bands in the carbonyl regionassigned to terminal carbonyl ligands. The discussion of the 'Hn.m.r. behaviour of these complexes is best deferred until afterthe X-ray crystal structure of (8) is discussed.Of (6) established that J(PtPA) = -209, J(PtPB) = +2 600,Crystal Structure of [(OC),Fe(p-dppm)(q4-(CH2)(CMe,)-CPt(PPh,)}] (8).-Crystals of (8) were grown by sloJ.CHEM. SOC. DALTON TRANS. 1988 1189e:Figure 3. Molecular structure of [(OC),Fe(p-dppm){q4-CH2)(CMe2)-CPt(PPh,) ) ] (8) showing the principal atomic numberingevaporation of a dichloromethane-n-hexane (1 : 3) solution.The structure is shown in Figure 3 and selected intramoleculardistances and angles are in Table 6. The iron and platinummoieties are linked by a single dppm bridge to give a five-membered FePCPPt ring with an Fe-Pt distance of 261.8(4)pm, indicating a metal-metal bond. The dimethylallene ligand isbridging the Fe-Pt bond and is o-co-ordinated to Pt and q3-c0-ordinated to Fe. The molecule is most informatively viewed as aphosphine-substituted platinatrimethylenemethane complex inwhich the (CH,)(CMe,)CPt(PPh,)(dppm-P) moiety is q4-co-ordinated to Fe.Comparison of the bonding parameters of(8) with those of [Fe(CO),{C(CH,),}] itself show a closeagreement, allowing for the effect of the longer Fe-Pt distance in(8) with respect to an Fe-C distance. Thus, in (8) the C(3)-C(4)and C(4)-C(5) distances are 142.1(9) and 142.6(9) pm respec-tively while in [Fe(CO),{C(CH,),}] the C-C bond lengthsare 143.7 pm.'" In the latter the Fe-C(outer) distance of 212.3(5)pm is greater than the Fe-C(centra1) distance of 193.8(5) pm.These bond lengths are similar to the analogous lengths in (€9,uiz. the Fe-C(5) and Fe-C(3) distances of 221.1(8) and 214.4(8)pm are longer than the Fe-C(4) distance of 197.1(7) pm.TheFePCPPt five-membered ring warrants further comment. It isseverely distorted, with the phosphorus atom P(l) lying wellbelow the plane made by Pt-C(4)-Fe. This contrasts with thestructures of (3) and (5) in which the dppm bridging ligand liesnearly in the plane made by the metals and the organic ligand.The structure of (8), therefore, illustrates the great flexibility ofthe dppm bridge in accommodating unusual bonding arrange-ments which cause steric constraints.The 'H n.m.r. spectrum of complex (6) is temperaturedependent. At low temperature (- 20 "C) all of the protons ofthe allene ligand are non-equivalent and the methylene protonsof the dppm ligand are also non-equivalent.These observ-ations can be explained by assuming that the low-temperaturespectrum reflects the solid-state structure and that the solid-state structure of (6) is analogous to that determined for (8) [thisis reasonable as the 31P-(1H) n.m.r. and i.r. parameters for (6)and (8) are similar]. Thus, the distorted diphosphine backboneeffectively leads to the inequivalence of the allene protons atlow temperature. At high temperature, the 'H n.m.r. spectrumof (6) shows only two types of allene proton and the dppmmethylene protons are now equivalent. This can be explained byenvisaging a rapid flipping of the FePCPPt ring, i.e. there will---Table 6. Selected distances (pm) and angles (") between interatomicvectors for [(OC),Fe(p-dppm){ q4-(CH2)(CMe2)CPt(PPh3)}] (8)Fe-PtP(3)-PtP(2)-FeC(2)-FeC(4)-FeO( 1 )-C( 1)C(4)-C(3)C(6)-C(5)C( 13)-P( 1)P( 3)-Pt-FeC(4)-Pt-P(3)C( 2)-Fe-P tC( 3)-Fe-PtC(3)-Fe-C(2)C(4)-Fe-C( 1 )C(4)-Fe-C( 3)C( 5)-Fe-C( 1)C(5)-Fe-C(3)C( 13)-P( 1)-PtP(2)-C(13)-W)O( 2)-C( 2)-FeFe-C (4)-PtC( 3)-C(4)-FeC(5)-C(4)-FeC(4)-C(5)-FeC(6)-C(5)-C(4)C( 7)-C( 5)-C(4)261.8(4)226.4(3)218.9(4)176.6(9)197.1 (7)185.2(7)1 16.4( 8)142.1(9)152.3( 1 1)150.5102.5(2)163.6(2)73.3 (2)90.3(3)119.0(4)40.1(2)90.2(3)68.8(3)105.3(3)1 10.0(4)178.3(5)8 1 3 3 )76.5(4)61.2(4)119.2(7)123.5(7)7934)C(4)-Pt-FeC( 1 )-Fe-P tC(2)-Fe-C( 1)C(3)-Fe-C( 1)C(4)-Fe-PtC(4)-Fe-C( 2)C( 5)-Fe-PtC( 5)-Fe-C(2)C(5)-Fe-C(4)C( 13)-P(2)-FeO( 1)-C( 1)-FeC(4)-C( 3)-FeC( 3)-C( 4)-P tC( 5)-C(4)-PtC(5FC(4)-C(3)C(6)-C(5)-FeC(7)-C(5)-FeC(7kC(5)-C(6)227.4(3)204.1 (7)175.6(9)214.4(8)221.1(8)185.3(7)1 16.0(8)142.6(9)151.8( 11)48.I( 1)97.1(3)98.6(4)I58.3(2)50.4(3)116.8(3)76.5(3)98.9(3)39.4(2)113.3(3)177.3(5)63.4(4)110.7(5)119.3(5)119.5(6)117.4(5)113.8(5)112.0(6)be a plane of symmetry through Pt, C(4), and Fe at an inter-mediate stage which makes the two allene protons cis toplatinum equivalent and the two allene protons trans toplatinum equivalent. Obviously such ring flipping has no effecton the 'H n.m.r. spectra of complexes (7) and (8) due to thesubstituents on the allene ligands. These spectra, therefore, aresimilar to that of (6) at - 20 "C except that one or two of theresonances due to the allene protons are absent.Protonation of (5) with HBF,*OEt, in dichloromethanegave the previously described p-propenyl complex [(OC),Fe-(p-dppm){ p-C(Me)=CH,}Pt(PPh,)][BF,] (9).The complexwas characterised by comparison of its 3'P-{'H} and 'Hn.m.r. and i.r. spectra with those of an authentic sample.' Thisresult links the allene systems with the acetylene systemspreviously reported, uiz. protonation of the propyne complex[(OC),Fe(p-dppm)(p-C(O)C(Me)CH)Pt(PPh,)] also gave (9),exclusively. ' Interestingly, protonation of the p-allene complex[Mo2(q 5-C5H 5)2(CO)4(p-CH,=C=CH2)] has been reportedto give the p-alkenyl cation ' ' [Mo,(q5-C5H5),(CO),(p-CH=C(H)Me}] + and not [Mo2(q 5-C5H,),(CO)4( p-C(Me)=CH,}] + which must be formed initially.Possibly, isomerisationto give the thermodynamically most favoured product canaccount for the results in both the Fe-Pt and Mo, systems.ExperimentalGeneral methods were as previously described in recent papersfrom this laboratory. l 2 The complexes [(OC),Fe(p-dppm)-(p-CO)Pt(PPh,)] and [(OC),Fe(p-vdpp)(p-CO)Pt(PPh,)]were prepared by previously described methods. 'Preparations.-[( OC),Fe( p-dppm) { p-C( 0)CH ,C(=CH ,)} -Pt(PPh,)] (3). A solution of [(OC),Fe(p-dppm)(p-C0)Pt-(PPh,)] (1) (0.30 g, 0.30 mmol) in dichloromethane (3 cm3) wassaturated with allene. The mixture was set aside at ca. 20 "C for5 d, after which time a yellow solid had precipitated.Addition ofan excess of diethyl ether and refrigeration (- 5 "C) overnigh1190 J. CHEM. SOC. DALTON TRANS. 1988Table 7. Crystallographic data *CompoundCrystal dataFormulaMSystemalpmblpmclpmai"Pi"Y/"U/nm3ZSpace groupDJg cm-,l/cm-'F(000)(3)C5,H4 FeO,P,Pt1049.22Orthorhombic2 481.5(3)1906.2(2)1 838.7(3)8.6988Pbca1.60233.354 144Data collectionScan width (" + rx-doublet splitting)Total data 6 448No. observed [I > 20(1)] 4 4011.8Unique data 5 455RefinementgRR'No. of parameters0.00020.03 150.0302456C,,H,,FeO3P,Pt1021.71Monoclinic1 195.1(2)2 258.5(3)1673.9(4)108.15(2)4.48341.51334.262 012P2,ln2.05 9585 4064 8350.00030.02860.029545 1* Details common to all three structures.Scan speed 2.c29.3" min-'; 28 (min., max.) 4.0, 45.0°.C,,H,,FeO,P,Pt1021.76Monoclinic1098.4(3)1 889.8(6)2 216.3(5)103.52(2)4.72941.43534.3 32 024p2 1 Ic2.06 2345 7015 0800.00030.03 1 10.03 16432Table 8. Atom co-ordinates ( x lo4) for compound (3)AtomPtFeP(1)P(2)P(3)C(111)C(112)C(113)C( 114)C(115)C(116)C(121)C(122)C(123)C( 124)C( 125)C( 126)C(13)C(211)C(212)C(213)C(214)C(215)C(216)C(221)C(222)C(223)C(224)C(225)X3 41 5.0( 1)4 297.9(4)3 560(1)4 535(1)2 772( 1)2 920(1)2 672(1)2 156(1)1888(1)2 136(1)2 652( 1)3 906(2)4 240(2)4 548(2)4 522(2)4 188(2)3 880(2)3 959(2)5 070(1)5 427(1)5 831(1)5 877(1)5 520(1)5 116(1)4 785(2)4 440(2)4 634(2)5 173(2)5 518(2)Y Z3 519.0(1) 1 405.4( 1)2 852.1(5) 1869.7(5)3 183(1) 206( 1)2 416(1) 782( 1)4 371(1) 1 277(1)2 915(2) - 191(2)2 320(2) 96(2)2 132(2) - 133(2)2 539(2) - 649(2)3 135(2) - 937(2)3 323(2) - 708(2)3 708(2) - 478(2)4 254(2) - 250(2)4 622(2) - 757(2)4 444(2) - 1 492(2)3 898(2) - 1 720(2)3 529(2) - 1 213(2)2 368(3) 160(4)2 882(2) 289(2)3 292(2) 691(2)3 670(2) 338(2)3 638(2) -417(2)3 228(2) -820(2)2 850(2) - 467(2)1 509(2) 796(3)974(2) 1025(3)29 l(2) 1 lOl(3)143(2) 948(3)677(2) 719(3)AtomC(226)C(311)C(312)C(3 13)C(314)C(315)C(316)C(321)C(322)C(323)C(324)C(325)C(326)C(331)C(332)C(333)C(334)C(335)C(336)C(1)O(1)C(2)O(2)C(3)O(3)C(4)(34)C(5)X5 323(2)2 987(2)3 503(2)3 698(2)3 376(2)2 860(2)2 665(2)2 592(2)3 016(2)2 911(2)2 382(2)1957(2)2 062(2)2 llO(2)1850(2)1341(2)1093(2)1352(2)1861(2)3 740(3)3 399(2)4 862(3)5 246(2)4 488(3)4 619(2)4 174(3)4 487(3)3 684(3)Y1 360(2)5 190(2)5 224(2)5 858(2)6 458(2)6 424(2)5 790(2)4 729(2)4 960(2)5 241(2)5 292(2)5 061(2)4 780(2)4 135(2)4 497(2)4 283(2)3 707(2)3 345(2)3 559(2)2 284(4)1858(3)2 433(4)2 154(3)3 724(4)4 3 15(3)3 219(4)3 135(4)3 663(4)Z643(3)2 01 l(2)1713(2)2 284(2)2 259(2)1960(2)1687(2)38 l(2)- 55(2)-741(2)-991(2)- 555(2)131(2)1634(3)2 192(3)2 425(3)2 lOO(3)1542(3)1308(3)1908(4)1 917(3)2 231(4)2 456(3)1 708(4)1632(3)2 881(4)3 392(2)3 022(4)gave the desired product as pale yellow microcrystals. Yield 0.11 [(OC),Fe(p-dppm){p-C(=CH2)CH2)Pt(PPh,)] (5).A sol-g, 35%. The vdpp analogoue [(OC),Fe(p-vdpp)(p-C(O)CH,C- ution of [(OC),Fe(p-dppm)(p-CO)Pt(PPh,)l (0.3 1 g, 0.3 1(=CH,))Pt(PPh,)] (4) was prepared in a similar manner from mmol) in benzene (20 cm3) was refluxed for 10 min, with allene[(OC),Fe(p-vdpp)(p-CO)Pt(PPh,)l (2), in 27% yield. slowly bubbling through the solution. The resultant solutioJ. CHEM. SOC. DALTON TRANS. 1988 1191Table 9. Atom co-ordinates ( x lo4) for compound (5)AtomPtFeP(1)P(2)P(3)C(111)C(112)C( 113)C( 114)C(115)C( 116)C( 121)C( 122)C( 123)C( 124)C( 125)C( 126)C(13)C(211)C(212)C(213)C(214)C(215)C(216)C(221)C(222)C( 223)C( 224)C( 225)X- 370.5(2)1 497(1)882( 1)- 1 428(1)-1 619(1)- 2 087(3)- 3 154(3)- 3 009(3)- 1 943(3)- 1 481(3)-2 567(3)-2 855(3)- 3 626(3)-4 109(3)-3 821(3)- 3 050(3)- 488(4)-3 615(3)63 l(4)- 433(4)-617(4)264(4)1328(4)1 511(4)1776(3)1936(3)3 047(3)3 523(3)1 300(3)Y1 346.2(1)1987.5(3)1 800(1)2 528( 1)625( 1)1294(2)1403(2)1008(2)505(2)396(2)791(2)2 335(1)2 332( 1)2 738(1)3 147(1)3 151(1)2 745( 1)2 236(2)3 332(1)3 517(1)4 094( 1)4 485( 1)4 299( 1)3 723(1)2 545(2)2 783(2)2 770(2)2 518(2)2 280(2)Z2 246.1(1)2 428.2(4)1 007(1)1270(1)2 398(1)123(2)- 498(2)- 1 137(2)- 1 154(2)- 533(2)106(2)1075(2)1821(2)1955(2)1 344(2)598(2)463(2)535(3)1386(3)1 474(3)1 575(3)1587(3)1498(3)1398(3)555(2)- 242(2)- 8 1 3(2)- 588(2)209(2)AtomC(226)C(3 1 1)C(312)C(3 13)C(314)C(3 15)C(316)C(321)C(322)C(323)C(324)C(325)C(326)C(331)C(332)C(333)C(334)C(335)C(336)C(1)O(1)C(2)O(2)C(3)O(3)C(4)C(5)C(6)X2 888(3)-1 514(3)-1 563(3)-1 587(3)-1 561(3)-1 512(3)- 1 488(3)-3 223(2)-3 719(2)-4 920(2)- 5 626(2)-5 129(2)- 3 928(2)-1 348(3)- 2 18(3)32(3)- 849(3)- 1 980(3)- 2 229( 3)1 660(5)1754(4)575(5)26(4)2 875(6)3 769(4)883(6)1960(5)3 040(6)Y2 293(2)482(1)- 62( 1)- 132(1)341(1)885(1)955(1)716(2)613(2)702(2)893(2)996(2)907(2)-115(1)- 235( 1)- 765( 1)-1 176(1)- 1 056(1)- 526( 1)1356(3)949(2)2 359(3)2 609(2)2 343(3)2 564(3)1089(4)1377(3)1227(4)z780(2)3 497(2)3 814(2)4 636(2)5 142(2)4 825(2)4 003(2)1 917(2)1058(2)669(2)1 139(2)1998(2)2 387(2)2 OW311972(3)1701(3)1457(3)1485(3)1756(3)1 849(3)1461(3)2 929(3)3 269(3)2 840(4)3 142(3)3 367(4)3 882(5)3 379(3)Table 10.Atom co-ordinates ( x lo4) for compound (8)AtomPtFeP(1)P(2)P(3)C(I11)C( 112)C(113)C( 114)C(115)C( 116)C(121)C( 122)C( 123)C( 124)C( 125)C( 126)C(13)C(211)C(212)C(213)C(214)C(215)C(216)C(22 I )C(222)C(223)C(224)C(225)X2 305.0(2)13 844.4(7)570( 1)175( 1)3 960(1)- 170(3)- 450(3)-937(3)- 1 144(3)- 864(3)- 377(3)497(3)1608(3)I 570(3)421(3)- 690(3)- 652(3)- 609(5)850(3)1628(3)2 222(3)2 040(3)1 262(3)668(3)- 1 292(3)- 1 732(3)- 2 874(3)-3 575(3)-3 135(3)Y2 211.2(1)97 1.0(4)2 902( 1)1 607(1)2 916(1)3 165(2)3 869(2)4 046(2)3 519(2)2 815(2)2 639(2)3 714(2)4 004(2)4 582(2)4 871(2)4 582(2)4 003(2)1987(2)1542(2)1795(2)2 494(2)2 939(2)2 686(2)1 194(2)567(2)283(2)625(2)1252(2)2 344(3)Z952.4( 1)1 130.0(4)833( 1)1 575(1)929( 1)35(1)- 132(1)- 753( 1)- 1 206(1)- 1 039(1)-418(1)1269(2)1618(2)2 005(2)2 042(2)1692(2)1306(2)1083(2)2 347(1)2 772(1)3 358(1)3 519(1)3 095( 1)2 509(1)1695(2)1388(2)1443(2)1805(2)2 112(2)AtomC(226)C(311)C(312)C(313)C(314)C(315)C( 3 1 6)C(321)C(322)C(323)C(324)C(325)C(326)C(33 1)C(332)C(333)C(334)C(335)C(1)O(1)C(2)O(2)C(3)C(4)C(5)C(6)C(7)C(336)X- 1 994(3)5 023(3)5 436(3)6 21 l(3)6 572(3)6 158(3)5 383(3)54 496(3)5 230(3)6 468(3)6 972(3)6 238(3)3 660(3)4 298(3)4 053(3)3 171(3)2 778(3)279(6)1158(5)1042(5)3 185(5)3 121(5)2 723(6)3 373(6)2 534(3)-428(4)2 900(5)Y1536(2)2 595(2)1897(2)1615(2)2 032(2)2 731(2)3 012(2)3 028(2)2 939(2)3 071(2)3 293(2)3 382(2)3 250(2)3 824(2)4 414(2)5 083(2)5 160(2)4 570(2)3 901(2)920(3)863(2)122(3)1040(3)1240(3)713(3)940(4)-437(3)- 42(4)2 057(2)457(2)548(2)191(2)- 256(2)- 347(2)1 O(2)2 811(1)1 700(1)2 218(1)2 887(1)2 370(1)1 776(1)636(2)929(2)661(2)9 9 w74m- 194(2)416(3)1419(3)1613(3)1761(3)1 136(3)662(3)767(4)- 62(2)- 12(3)was cooled to ca.2OoC, filtered, and concentrated under was then cooled to ca. 20°C and the solvent removed underreduced pressure to give the desired product as pale yellow reduced pressure. The residue was extracted into hot n-hexanemicrocrystals. Yield 0.18 g, 57%. (100 cm3) and the solution concentrated under reduced[(OC),Fe(p-dppm)(q4-(CH2)2CPt(PPh,))] (6). A solution pressure, to give the desired product as yellow microcrystals.of [(OC),Fe(p-dppm)(p-C(=CH2)CH2}Pt(PPh,)](5) (0.1 g, 0.1 Yield 0.07 g, 72%.[(OC), WP-dpPm) { q 4-(CH2)(CH Ph)C pt(p Ph 3 1) 1 (7).A mmol) in benzene (20 cm3) was refluxed for 2 h. The mixtur1192 J. CHEM. SOC. DALTON TRANS. 1988solution of [(OC),Fe(p-dppm)(p-CO)Pt(PPh,)l (0.30 g, 0.30mmol) and 3-phenyl-1,2-propadiene (0.06 g, 0.05 mmol) inbenzene (20 cm3) was refluxed for 1 h. The solution was cooledto ca. 20 "C and the solvent removed under reduced pressure.The residue was extracted into hot n-hexane (100 cm3) and thesolution concentrated under reduced pressure, to give thedesired product as yellow microcrystals. Yield 0.18 g, 56%.solution of [(0C),Fe(p-dppm)(p-CO)Pt(PPh3)] (0.40 g, 0.40mmol) and 3-methyl-1,2-butadiene (0.14 g, 2 mmol) in dichloro-methane (20 cm3) was refluxed for 48 h.The solution was cooledto ca. 20°C and the solvent removed under reduced pressure.The residue was extracted into hot n-hexane (130 cm3) and thesolution concentrated under reduced pressure to give thedesired product as yellow microcrystals. Yield 0.27 g, 66%.C(oC>2Fe(~-dPPm)~r14-(~~2)(CMe,)CPt(~~~3~~l (8). AX- Ray Crystallography.-All crystallographic measurementswere made on a Nicolet P3/F diffractometer operating in thew-28 scan mode using graphite-monochromatised Mo-K,radiation (h = 71.069 pm) following a standard proceduredescribed in detail e1~ewhere.l~ All three data sets werecorrected for absorption empirically once their structures hadbeen determined,14 and the three structures were solved viastandard heavy-atom methods and refined by full-matrix leastsquares using the SHELX program system.' The refinementwas essentially the same for all three complexes with all non-hydrogen atoms being assigned anisotropic thermal parametersand the phenyl groups treated as rigid bodies with idealisedhexagonal symmetry (C-C 139.5 pm).In each case themethylene and phenyl hydrogen atoms were included incalculated positions (C-H 108 pm) and an overall isotropicthermal parameter was assigned for each group. The hydrogenatoms on the allene groups were located experimentally for allthree complexes although for compound (8) these were notrefined. The weighting scheme w = [ci2(F') + g(Fo)2]-' wasused for all three compounds in which the parameter g wasincluded in refinement in order to obtain satisfactory agreementanalyses.All relevant crystal data, data collection and structurerefinement parameters are listed in Table 7, whilst non-hydrogen atomic co-ordinates for compounds (3), (S), and (8)are given in Tables 8, 9, and 10 respectively.Additional material available from the Cambridge Crystallo-graphic Data Centre comprises H-atom co-ordinates, thermalparameters, and remaining bond lengths and angles.AcknowledgementsWe thank the S.E.R.C. for support and Johnson Matthey Ltd.for the generous loan of platinum metal salts.ReferencesX. L. R. Fontaine, G. B. Jacobsen, B. L. Shaw, and M. Thornton-Pett, J. Chem. Soc., Dalton Trans., 1988, 741.W. I. Bailey, jun., M. H. Chisholm, F. A. Cotton, C. A. Murillo, andL. A. Rankel, J . Am. Chem. Soc., 1978, 100, 802.L. N. Lewis, J. C. Huffman, and K. G. Caulton, Znorg. Chem., 1980,19, 1246.E. L. Hoel, G. B. Ansell, and S. Leta, Organometallics, 1986, 5, 585.P. Racanelli, G. Pantini, A. Immirzi, G. Allegra, and L. Porri, Chem.Commun., 1969, 361.X. L. R. Fontaine, G. B. Jacobsen, B. L. Shaw, and M. Thornton-Pett, J. Chem. Soc., Chem. Commun., 1987, 662.R. E. Colborn, D. L. Davies, A. F. Dyke, A. Endesfelder, S. A. R.Knox, A. G. Orpen, and D. Plaas, J. Chem. Soc., Dalton Trans., 1983,2661.8 'International Tables for X-Ray Crystallography,' Kynoch Press,Birmingham, 1974, vol. 3.9 N. M. Doherty, M. L. Fildes, N. J. Forrow, S. A. R. Knox, K. A.Macpherson, and A. G. Orpen, J. Chem. Soc., Chem. Commun.,1986, 1355.10 A. Almenningen, A. Haaland, and K. Wahl, Acta Chem. Scand., 1969,23, 1145.1 1 A. F. Dyke, S. A. R. Knox, M. J. Morris, and P. J. Naish, J. Chem.Soc., Dalton Trans., 1983, 1417.12 S. W. Carr, B. L. Shaw, and M. Thornton-Pett, J. Chem. Soc., DaltonTrans., 1985, 2131.13 A. Modinos and P. Woodward, J. Chem. SOC., Dalton Trans., 1974,2075.14 N. Walker and D. Stuart, Acta Crystallogr., Sect. A , 1983, 39, 158.15 G. M. Sheldrick, SHELX 76, Program System for X-Ray StructureDetermination, University of Cambridge, 1976.Received 22nd June 1987; Paper 7/110

ISSN:1477-9226    

DOI:10.1039/DT9880001185

出版商:RSC    

年代:1988

数据来源: RSC