摘要:

J. CHEM. SOC. DALTON TRANS. 1994 2223Reduction of Nitric Oxide by Tetramesityliridium(1v) andCobaltocene. Reactions of Hyponitrite Complexes and ofthe Ether [CO(~~-C,H,)(~~-C,H,)](~-O-~XO) withNitroalkanes, Acids and Amines tRobyn S. Hay-MotherwelLa Geoffrey Wilkinson,*ra Tracy K. N. Sweet6 andMichael B. Hursthouse**6a Johnson Matthey Laboratory, Chemistry Department, Imperial College, London S W7 2A Y, UKSchool of Chemistry and Applied Chemistry, University of Wales Cardiff, PO Box 912, Cardiff CFl 3TB, UKThe interactions of either Ir(mes), (mes = C,H,Me,-2.4.6) or Co(cp), (cp = q5-C5H5) with NO in lightpetroleum gave unstable solids the IR spectra of which allow them to be formulated as hyponitritecomplexes, e.g. [Co(cp),],(N,O,) 1; their reaction with MeNO, is described.The compound Co(cp),with either NO or Ag,N,O, in toluene gave N,O and thevery reactive ether [Co(cp) (q4-C,H,)],(p-O-exo) 2.This reacts with nitroalkanes where the product depends on the nature of the nitroalkane. Nitromethaneproduced both Co(cp),+ CH,=NO>H,O 3 and [Co(cp)(q4-C5H5)],[(p-CH(N0,)-exo] 4, whileMe,CH (NO,) gave Co(cp) [q4-C,H,(CMe,N0,)-exo] and EtNO, corresponding species to 3 and 4(ie. 6 and 7). Reactions of 2 with alcohols or phenylacetylene gave mononuclear species of the sametype as 4; treatment with NH,Ph or NHPh, also gave similar ex0 complexes 8 and 9 respectively. Allthese exo species reacted with CHCI, to give the exo-CCI, compound by facile C-C bond cleavage.Mechanisms for the various reactions are discussed. The structures of compounds 2-4, 8 and 9 havebeen confirmed by X-ray crystallography: 2 and 4 contain Co(cp) (q4-C5H,) moieties bridged by oxygenor CH(N0,) groups while8 and 9 are monomers with exo-NHPh or -NPh,groups.In all cases but one (2)there are near-eclipsed C5CoC, geometries; for one of the cobalts in 2 there is a twist of ca. 16" from theeclipsed configuration. Compound 3 has Co(cp),' and CH,NO; ions the latter being involved in stronghydrogen bonding with the H,O molecule also present in the lattice. In both 8 and 9 there is structuralevidence for 7c interaction between p lone pairs on the planar nitrogen atom and the 7c system of aphenyl ring.This study arose from the observation that the paramagnetic(le) compound Ir(mes),, where mes = C6H2Me3-2,4,6,' re-acted with nitric oxide in light petroleum to give an unstablesolid, which was soluble in nitromethane or acetonitrilegiving a solution 'H NMR spectrum identical to that of theiridium(v) cation ' [Ir(mes),] +.Previous studies of the reactions of paramagnetic (le) alkylsand aryls of transition metals with nitric oxide led to insertionof NO into the M-C bond followed by the formation of anM=O bond and RN=NR.However, it was evident that despitethe existence of (mes),IrV=03 the reaction, equation (I), does(mes),lr=O + f(mes)N=N(mes) (1)not occur. In view of the limited quantities of Ir(mes), availablewe studied the reaction of NO with Co(cp)? (cp .=.q5-C,H,)which also is paramagnetic (le) and is readily oxidised to thecobaltocenium ion, CO(CP)~ +.,Studies by Bottomley and co-worker~,~ of paramagneticq '-cyclopentadienyl compounds of Ti" and V" showed that-f Supplementary data available: see Instructions for Authors, J.Chem.Soc., Dalton Trans., 1994, Issue 1, pp. xxiii-xxviii.the interaction with NO led to compounds with M-O-Mbonds. Although the dioxodinitrate(N-N)(2 - ) (hyponitrite)ion, N2022-, was considered as a possible intermediate inthe reactions, no direct evidence for the formation of this ionwas obtainedsc although N20 was formed; this gas could beobtained by the reaction (2). Unstable hyponitrite complexesof several transition metals have been obtained in reactions ofNO with low-valent metal compounds or in thermal reactionsof bis(nitrosy1) complexes.6 Sodium hyponitrite is made ' bysodium reduction of NO in reactions presumably involving twoone-electron transfers, equations (3)--(5).M' + 'NO - Mf + NO- (3)(4) NO- + 'NO - N,02'-N202'- + M' - 2M+N20Z2- ( 5 )Results and DiscussionReaction of Ir(mes), and Co(cp), with NO.-The inter-action of Ir(mes), with NO in light petroleum gives a green-black precipitate the IR spectrum of which, taken as quickly a2224 J.CHEM. soc. DALTON TRANS. 1994(vdii) I / I (vi) + ( V Q 4L-exo-CCI3 4 L-exo -CMe2N02Scheme 1 Main reactions of Co(cp), involving NO and nitroalkanes.L = (q5-C,H,)Co(q4-C,H,) unit. (i) NO in light petroleum; (ii) NO inMeNO,; (iii) NO or Ag,N,O, in toluene; (iu) toluene; (u) MeNO, inEt,O; (vi) Me,CH(NO,) in Et,O; (uii) CHCl,; (uiii) CCl, [SO% yield +Co(cp),CI].Nitrous oxide is eliminated in reactions of compound 1and in (iii)Fig. 1 Structure of the ether [Co(cp)(q4-C,H,)],(pO-exo) 2I IIpossible, has three bands (1097, 1022, 802 cm-') in the regionsfound for co-ordinated hyponitrites; ionic hyponitrites8 havetwo bands around 1058 and 571 cm-', as we have confirmedalso for Ag2N202. Since three bands are also found for thecobalt compound discussed below we consider that the iridiumcompound is the oxygen-bridged species [IrV(mes)4] 2(p-ONNO-K~O) formed by two one-electron transfers fromIr(mes), to NO as in equations (3)-(5).The interaction of Co(cp), (see Scheme 1) in hexane or lightpetroleum with NO leads rapidly to a beige precipitate.Thiscompound 1 is unstable at room temperature, becoming red-orange (see below), but the IR spectrum, again taken as rapidlyas possible, also has three bands at 1088, 1020 and 800 cm-' inaddition to bands for cp and q4-C5H, rings; a structure of thetype I seems reasonable.It is surprising considering the extensive work on reactionsof NO with M(cp), type compounds and especially in view ofthe innumerable studiesg on Co(cp), that the reaction of thelatter with NO appears not to have been reported, perhapsbecause of the problems encountered in this study. The onlycomparable reaction is that of Co(cp), and O2 at lowtemperatures,' which gives a very thermally unstable com-pound (decomp. > -40 "C), formulated only on the basis ofits chemical reactions (cf.later discussion) as the exo-peroxo-bridged q4-cyclopentadiene cobalt(1) complex 11. It may benoted here, in view of the similar compounds discussed below,that a variety of exo-bridged species are k n o ~ n , ~ ~ ' ~ e.g. with p-CF,CF, and p-CH,C(O)CH,; some are noted later.On standing in toluene compound 1 decomposes with lossof N20, confirmed by collection of gas and subsequent gaschromatography-mass spectrometry (GS-MS) study, to givean orange solution containing a cobalt(r) complex 2 describedbelow.The iridium hyponitrite dissolves in nitromethane withevolution of N20 as confirmed by mass spectral study but,unlike the cobalt system discussed below, no crystalline productcould be obtained; the 'H NMR spectrum in CDCl, of the solidresidue after pumping off MeN02 showed only bands forQOQ I I[Ir(mes),] + as noted in the Introduction and the IR spectrumshowed OH stretches.Reaction of Co(cp), and NO in Toluene.-By contrast withthe reaction in hexane, in toluene NO reacts immediately togive an orange solution (N20 is also formed and detected inoff-gas by mass spectrometry) from which, on cooling, orangecrystals of a compound 2 can be isolated. That a hyponitriteintermediate is involved is confirmed directly by vigorousstirring of a toluene solution of Co(cp), with solid Ag2N20,which again leads to 2 and N20.The compound 2 although stable at room temperature foronly ca.1 h can be kept below ca. -20 "C and the crystalstructure was determined at low temperature.This shows that 2is the exo-p-0 ether I11 and similar to that proposed for thep-peroxo species noted above. The structure is shown in Fig. 1and selected bond lengths and angles are given in Table 1. Themain feature is the unsymmetrical disposition of the q4-C,H,groups about the ether linkage which is probably due to stericeffects. As a result, the methine H atom on ring 2 [at C(201)]lies approximately over the q4 ring 1 [C(lO2)-C(lO5)] and theC-0-C angle at the ether oxygen at 114.7(3)0 is slightly largerthan expected. Other points of note relate to the geometries ofthe distorted rings. Not unexpectedly the q4 ring has 'slipped' asa result of the loss of bonding to the aliphatic carbons C(101)and C(201) by approximately 0.25 A.For Co( 1) the two ringshave a closely eclipsed relative arrangement whereas for Co(2)they are twisted by approximately 16" from an eclipsedconfiguration. The Co-C bond lengths to the q5 rings lie in therange 2.037(5)-2.082(5) 8, whereas the distances to the q4 ringsare significantly shorter on average and specifically shorter tothe central atoms of the 'butadiene' fragment [C(103), C(104)and C(203), C(204)] at 1.967(5)-1.974(5) A, cf 2.027(5)-2.042(5) 8, to C(102), C(105), C(202) and C(205). The C-0distances in the ether link at 1.456(5), 1.475(5) A are normal. IJ. CHEM. SOC. DALTON TRANS. 1994 2225Table 1 Selected bond lengths (A) and angles (") for compounds 2 4 , s and 9Co( 1 )-c( 101)Co( 1)-c( 102)Wl)-c(104)Co( 1)-C( 103)Co( 1 w ( 105)Co( l)-C( 106)Co( 1 w ( 107)Co( 1 )-C( 108)Co( 1 )-c( 109)Co(l)-C(110)CO(2)-C(201)CO(2)-C(202)Co(2)-C(203)Co( 2)-c(204)Co(2)-C(205)Co( 2)-C(206)Co( 2)-C(207)Co( 2)-C(208)Co( 2)-C(209)CO(2)-C(2 10)Solvent in latticeO( 1 )-N0 ( 2 t NC(1l)-NBridging atomsO( 1 )-C( 10 1)O(l)-C(201)C( 1 )-C( 10 1)C(l)-C(201)Pendant groupsN-C(l)N-C( 1 1)N-C(21)N-HX( 1 )-c( 10 1 )-C( 102)X( 1 )-C( 101)-C( 105)X( 1 )-C(20 1)-C(202)C(20 1 )-X( 1 )-C( 1 0 1)X( l)-C(201)-C(205)C( 104)-C( 105)-C( 101)C( 103)-C( 102)-C( 101)C(204)-C(205)-C(20 1 )C(203)-C(202)-c(201)N( 1 )-C( 1)-C(201)N( 1 )-c( 1)-C(101)0(2)-N-O( 1)O(2)-N-C( 1 1)O( 1 EN-C( 1 1)C(2)-C( 1 )-NC(5)-C( 1 )-NC(3)-C(2)-C(l)C(4FC(5)-C(l)C(l)-N-C(ll)C( 1 )-N-C( 2 1 )C( 1 )-N-HC( 1 1 )-N-H22.497(4)2.038( 5)1.974(5)1.968(5)2.042(5)2.044(5)2.037(5)2.078(5)2.082(5)2.046( 5)2.527(5)2.027(5)1.967(5)1.967(5)2.04 1 (5)2.055(5)2.061(5)2.077(5)2.078(5)2.050(5)---1.475(5)1.456(5)------1 17.3(4)1 17.0(4)110.7(4)114.7(4)114.7(3)109.4(4)109.9(4)110.1(4)108.9(4)-------------32.021 (4)2.019(4)2.0 17(4)2.010(4)2.01 5(5)2.010(4)2.005(4)2.023(4)2.022(4)2.0 12(4)----------1.303(4)1.276(4)1.308(5)----__-__------------1 1733)122.6(4)120.0(4)--------42.554( 5)2.027(5)1.980(5)1.967(5)2.008(5)2.030(5)2.039(5)2.092( 5)2.090( 5 )2.042(5)2.548( 5)2.027(5)1.964(5)1.973(5)2.008 (4)2.030( 5)2.052(5)2.100( 5)2.08 1 (5)2.028(6)-----1.540(6)1.554(6)----1 15.4(4)113.0(4)11 5.3(4)114.7(4)1 12.8(4)1 10.0(4)109.8(4)109.7(4)109.3(4)110.0(4)106.1 (3)123.4(4)117.9(4)1 18.8(4)--------82.552(7)2.023(7)1.974(7)1.981(7)2.019(8)2.053(7)2.063(7)2.093(7)2.088(7)2.042( 7)-----------------1.475(8)1.387(8)1.05(8)-__-------------117.7(5)113.2(6)110.2(6)112.1(7)122.7(6)1 18(4)-114(4)92.534( 3)2.046( 3)1.985(4)1.982(4)2.031(3)2.070(4)2.102(4)2.097(4)2.040( 3)2.066(4)-----------------1.508(4)1.400(4)1.450(4)---------------116.5(2)1 16.4(3)110.3(3)110.4(3)119.0(2)119.2(2)~-For compounds 3, 8 and 9, C(101) to C(110) refer to actual atoms C(l) to C(10); for 2, 4, 8 and 9, C(101) and C(201) (2 and 4) are the tiltedatoms in the q4 rings; X is the bridging atom, oxygen in complex 2 and carbon in 4; for compound 4, C( 1 1) refers to the actual atom C( 1).the folded q4 rings the envelope folds are 27.6(3) and 30.2(5)'for rings 1 and 2 respectively; the angles between the q5 ringsand q4 moieties are close to zero at 3.9(3) and 3.4(4)".The IR and 'H NMR spectra of compound 2 are in accordwith the ether structure and are closely similar to those of thecobalt and rhodium cyclopentadiene complexes M(cp)(q4-C,-H,R) [M = Co, R = H, Me, CHCl, or CCl,, M = Rh,R = HI; the cobalt compounds were made by interaction o2226 J.CHEM. soc. DALTON TRANS. 1994H i 0 3Fig. 2 Asymmetric unit in the structure of Co(cp),+CH,=NO,-*4cFig. 3 Packing diagram for compound 3alkyl halides with Co(cp),.*~"" The only difference is that 2has a band in the IR spectrum at 898 cm-' that can be assignedto the ether, C-0-C, linkage. The ether 2 is exceptionallyreactive towards compounds with acidic hydrogens and thisbehaviour is in striking contrast to the usual low reactivity* The compound Rh(cp)(C,H6) was made by direct interaction ofRhCl, and Na(cp) in the solid state at cu. 120 "C in November 1955 atHarvard University by G.W. and characterised by IR and 'H NMRspectroscopy. These species were first formulated as having endo-Rgroups but later reformulated as ex0 species.gb The mechanism ofreactions of Co(cp), and RX is known to be free radical in nature.' lb\, 4b..... \ / /Fig. 4 Hydrogen-bonded ribbons of H,O-CH,NO,- present in thestructure of compound 3of ethers, except special cases like alkyl tetrahydropyranylethers.Reactions of Compound 2 with Nitroa1kanes.-Nitromethanereacts rapidly with compound 2 in diethyl ether solutions {cf.the reaction of [1r(me~)~],(N,O,) with MeNO, above} togive two products easily separated by crystallisation. The ,firstisolated is a yellow crystalline solid 3 which is unstable at roomtemperature or on pumping in vacuum, losing MeNO,.Theresidue according to IR spectra appears to be Co(cp),+OH-.Since the crystal structure of 3 discussed below indicates that it isCo(cp), +CH,=NO, --H,O this observation is not surprising.In solution in CDCl, the 'H NMR spectrum shows bands forCo(cp),+ and MeNO,, the latter formed by reaction ofCH,=N02 - and the water of crystallisation.The structure of compound 3 determined by X-ray crystal-lography at low temperature is shown in Fig. 2; selecteJ. CHEM. SOC. DALTON TRANS. 1994 22272H4Scheme 2 Interaction of compound 2 with nitromethane. Overallstoichiometry, 2 x 2 + 3 MeNO - 2 x 3 + 4Fig. 5 Structure of [C~(C~)(~~-C~H~)]~[~-CH(NO,)-~XO] 4bond lengths and angles are given in Table 1.The rings inthe cobaltocenium ion have a near-eclipsed configurationwith Co-C bond lengths shorter than in the Co(cp) moiety forcompound 2 as expected, 2.005(4)-2.023(4) A. The compoundalso contains the methylideneazinate ion CH2=N02 - thestructure of which has not, to our knowledge, previously beendetermined.I3 The ion is planar to within limits of experimentalerror and the geometry agrees with the results of theoreticalcalculations, 3a except that our measured C-N bond, whichclearly has multiple character, is some 0.04 A shorter than thatpredicted using an extended basis set (MP2-HF/6-3 1 G*), butagrees very well with that computed at the Hartree-Fock (HF)level. The two N-O bond lengths are 1.276(4) and 1.303(4) A,with the former agreeing well with theory.In the crystalstructure the CH,=NO, - ion is involved in an extended ribbon-like hydrogen bonding system with the water molecule as canbe seen in Figs. 3 and 4. The strongest interactions are0(3)-H(32) O(I)-N 1.83 and 0(3)-H(31) O(I)-N 1.81A. The involvement only of O( 1) of the NO, group in hydrogenbonding probably accounts for the greater length of O( 1 )-N.The second compound 4 formed in the reaction of 2 withMeNO, is red-orange; this is the exo-CH(N0,) cyclopenta-diene cobalt(1) complex shown in IV. In addition to the bandscharacteristic for the cp and q4-diene rings the IR spectrumshows NO, stretches; the ‘H NMR spectrum in C,D, has atriplet for the H of the exo-p-CH(N0,) group while the endo-Hatoms of the rings appear as a doublet of triplets, the couplingconstant (J = 8.25 Hz) being as expected.The structure of compound 4 as determined by X-raydiffraction is shown in Fig.5; selected bond lengths and anglesare given in Table 1. It is analogous to that of 2 but with0 replaced by a doubly deprotonated MeNO, group, i.e.CH(N0,). The presence of the latter results in a differentconformational arrangement of the q4-C5H5 groups about theC-C bonds of the bridge and it is noteworthy that the C-C-Cangle is some 2’ less than the C-0-C angle in 2. The geometriesof the Co(cp) and q4-C,H5 fragments are very similar to thosein 2 in terms both of bond lengths (Table 1) and folds in the q4rings [33.0(5), 32.5(4)”]. However, the angles between the q5ring and the q4 fragment are now 6.4(5) and 6.8(3)”, the slightincrease possibly reflecting the greater steric crowding presentin 4.The rings are close to eclipsed in both fragments of themolecule.Reaction Mechanisms of NO and RNO, Reactions.-Assuming, as suggested above, that the hyponitrite is co-H\0 /”< + I/”\H, ,NO2/ \ / \ A H20 +Scheme 3 Carbonium ion route for interaction of compound 2 andMeNO,ordinated in compound 1 it seems most likely that the N,O,group is ex0 bound to a q4-cyclopentadiene ring as in V[equation (6)] since ready decomposition to the ether 2 and2N,O can then occur. Co-ordination of hyponitrite to cobaltseems highly unlikely. The reaction of 2 with MeNO, couldthen proceed as in Scheme 2. An alternative in Scheme 3involves carbonium ion intermediates.Although the hydroxospecies Co(cp)[q4-C5H5(OH)-exo] shown in Scheme 2 haspreviously been postulated in the interaction of Co(cp), + salt2228 J. CHEM. soc. DALTON TRANS. 1994with concentrated NaOH solutions under forcing conditions togive azulene in low yield14 there appears to be no otherevidence for its existence. The em-hydroxide would doubtlessreact immediately with MeNO, to give Co(cp)[q4-C,H,(CH,NO,)-exo] which, with a second molecule of thehydroxide, would produce the unique p-CH(N0,) bridge incompound 4. The water formed in the reactions is then found inthe salt 3.The formation of the monomeric exo-CH,NO, species as anintermediate in Scheme 2 suggested that treatment of compound2 with Me2CH(N02) would give only a monomer, since furtherH-atom transfer to give p-CH(N0,) could not occur.This wasfound to be the case and the em-CMe,NO, complex 5 wasisolated in essentially quantitative yield according to equation(7). It is of interest that in neat nitroalkanes as solvent2 5Co(cp), reacts with NO to give only the Co(cp),+ salts of theappropriate anion. Presumably the protonation reactionscoupled with the driving force of N,O elimination are morerapid than the reactions of the ether 2 with nitroalkanes.The ether 2 does, however, react with EtNO, to give boththe Co(cp),+ salt of Me(H)C=NO,- 6 as well as Co(cp){q4-C,H,[CH(Me)NO,-exo]} 7. The failure to form the analogueof compound 4 despite the presence of a CH group in 7 ispresumably due to steric factors.These are perhaps also thereasons why Me2CH(N0,) in Et,O gives only 5 without theformation of the cobaltocenium salt.Other Reactions of Compound 2.-There have been previoussyntheses of exo-q4-diene cobalt species from CH acids.Thus acetylene reacts with Co(cp), to give a dimeric specieswith an exo-CHSH bridge l 6 while secondary phosphineoxides HP(O)R,, e.g. R = Bu" or C6Hll, give Co(cp){q4-C,H,[P(O)R,-em]} and hydrogen at 100-140 OC.I7 However,most species [other than those formed along with Co(cp)X byinteraction of Co(cp), with halogenoalkanes, see e.g. refs. 9(a),(b) and 1 l(a)] have been obtained by interaction of Co(cp), inthe presence of oxygen with a variety of compounds 'v1' andevidently these reactions involved the labile p-peroxo speciesnoted earlier.exo-Compounds were obtained from CHC1, ,MeCN, Me,HCCN, PhCgH, Me,CO [which gives a CH,-C(O)CH, bridge] as well as CSH6,l8 C5H,Me, indene andmethanol.In addition to confirming the nature of some of theseproducts in reactions of compound 2 other new ones havebeen obtained. In all cases stoichiometric amounts of thereagent were added to the toluene solution of 2 made in situfrom NO and Co(cp), . The compounds were characterised by'H NMR spectra in benzene solution. Monomeric species wereobtained from PhCzCH,'Ob MeOH '' and adamantan-1-01.Acetic acid and C6F,0H however gave the Co(cp),+ salts ofthe anion while SiHPh, gave Co(cp)(C,H,) and (Ph,Si),O.There was no reaction with RhH(CO)(PPh,), .While Co(cp), can readily be obtained by interaction ofCoCl, with C,H6 in the presence of NEt, and NHEt,,19 intoluene compound 2 reacts with NH,Ph, NHPh,, NHEt,, 1-aminonaphthalene and carbazole.Although the complex fromcarbazole is insoluble, the other species are moderately solublein benzene and stable at room temperature. The structures of 8and 9 (Figs. 6 and 7), the exo compounds from aniline anddiphenylamine, respectively, have been determined by X-raycrystallography, selected bond lengths and angles are given inTable 1. The structures show that the geometries of theCo(cp)(q4-C,H,) moieties in 8 and 9 are similar to those ofthe other monomeric compounds of the types discussed earlier.W 5 )Fig. 6 Structure of Co(cp)[q4-C5H5-(NHPh>exo] 8/ \ Cf19HP4)Fig.7 Structure of Co(cp)[q4-C,H,-(NPh,)-exo] 9The envelope folds in the q4 rings are 31.7(6) and 29.3(3)" andthe cp/q4 rings are eclipsed in both molecules. Perhaps the mostsignificant feature in the structures is that in both molecules thegeometry about the N atom is planar with the one phenyl ring in8 and one of the rings in 9 coplanar with the plane of the sp2nitrogen. This feature and the shortness of the relevant N-Cbond length (especially in 9 where it is 0.05 A shorter than thatto the other ring which is orthogonal to the N plane) indicatessome interaction 2o between the n system of the coplanar phenylring and the lone pair on the N atom which is in the p orbitalperpendicular to the plane.Since the reaction of compound 2 with an amine is likely todiffer from that of CH acids, the attack is more likely to benucleophilic on the q4-diene ring than on the ether oxygenatom. A possible pathway is shown in Scheme 4.Facile C-X C1eauage.-Finally, all of the ex0 compoundsboth mono- and bi-nuclear except Co(cp)(C,H,) react rapidlyand quantitatively with CHCl, or CDCl, at room temperatureto give the exo-CC1, compound11a as, e.g., in equation (8).Possible mechanisms are of the type shown in equations (9)and (10).It is also of interest that the C-P bond in theMezC=NO(OH) - Me2CH(N02J. CHEM. soc. DALTON TRANS. 1994 2229f :NuH1 co(CP)CO(Cp)CO(CP)Overall reaction:Nu2+2NuH - 2 0 +H*OIco(CP)Scheme 4 Interaction of amines with compound 2.Reaction (iv)follows a path similar to those in (i)-(iii). Nu = NucleophileCo(~p)[CsHs(CCl3)] + PhCECH (10)n HC'c 13P(O)R, species noted above is also cleaved by CDCl," butthe products were formulated as having exo-CDC1, groupsaccording to the 'H NMR spectra, which of course wouldnot be definitive. We consider them also to have exo-CC1,groups.ExperimentalMicroanalyses for the compounds (with one exception) couldnot be obtained due to the air and thermal sensitivity. Thegeneral techniques used have been described. ' Infrared spectra(cm--') are in Nujol mulls. Proton NMR spectra (6 vs. SiMe,)were obtained on a JEOL-EX-270 spectrometer at 270 MHz,mass spectra of NO and N20 gas samples on a JEOL JMS-AX505W spectrometer by the University of London MS Service atKing's College.Commercial samples were from Aldrich.The light petroleumused had b.p. 40-60 "C. Nitric oxide was passed througha copper coil at -78 "C and the purity checked by massspectrometry. Sodium and silver hyponitrites ' v 8 and Co(cp), ''were made as described. Nitroalkanes were dried over CaSO,and distilled under N,. All operations were carried out underpurified N, or Ar or under vacuum.Interaction ~fCo(cp)~ and NO.-The gas was slowly passedthrough CO(CP)~ (ca. 0.2 g) in light petroleum (30 cm3) for 5-10min until the purple colour disappeared and a beige precipitateof compound 1 was formed. After rapid filtration, the IRspectrum showed bands due to hyponitrite (see text) in additionto q5- and q4-C,H5 bands; the N,02 bands disappear when thesolid turns red-orange to be replaced by the C-0-c bandz2 atca.900 cm-' due to the ether link in 2. The gas above the solidafter decomposition was N,O.When a similar reaction was carried out in toluene a smallamount of yellow solid was formed and a red-orange solutionfrom which, after filtration, reduction in volume to ca. 10 cm3and cooling ( - 20 "C), X-ray-quality crystals of [Co(cp)(q4-C,H,)],(p-O-exo) 2 were obtained in > 90% yield. The crystalsare stable for weeks at -20 "C. IR (cm-I): Co(cp)(q4-C,H,)bands 'la and 898 (C-0-C). 'H NMR (C6D6): 6 4.71 (t, JaV =1.5, 4 H, H3*4 of q4 ring), 4.44 (s, 10 H, cp), 4.03 (t, J,, = 2.3,2 H, endo H1 of q4 ring), and 3.04 [q, J (inner pair) = 2.0, J(outer pair) =2.3 Hz, 4 H, H2s5 of q4 ring].This spectrum isidentical to that of the complex obtained from decompositionof 1 in toluene at room temperature. Compound 2 was alsoobtained essentially quantitatively when a mixture of Ag,N,02(ca. 0.07 g) and Co(cp), (ca. 0.09 g) in toluene (30 cm3) wasstirred very vigorously for 1 h; N,O was lost and the solutionbecame red-orange with formation of a black precipitate ofsilver. After filtration and reduction in volume, compound 2was obtained in > 80% yield on cooling to - 20 "C.Reactions with Nitroalkanes.-(a) Compounds 3 and4. A freshsample of compound 2 (ca. 0.06 g) was dissolved in MeNO, (ca.2 cm3) and the orange solution layered with Et,O. After ca. 48 hat -20 "C yellow crystals of 3 (ca.0.04 g, yield ca. 98%) werecollected. The filtrate was evaporated in vacuum and the residuedissolved in toluene; cooling at - 20 "C gave orange-redcrystals of 4 (0.03 g, yield ca. 98%). X-Ray-quality crystals of 3were obtained by recrystallisation from MeN0,-Et,O and of 4from toluene. Compound 3: IR (m-') 3400 (br, H,O), ca. 1200(C=N02-)23a and strong bands2,' at 1417, 1012 and 868[Co(cp),']; 'H NMR (CDCl,) 6 5.8 (s, cp) and 4.3 (MeNO,from reaction with H,O, see text). Compound 4: IR (cm-')6 4.77 (m, 4 H, H314 of q4 ring), 4.38 (s, 10 H, cp), 2.99 (d ofpseudo-t, 2 H, Jd = 8.25, J, = 2.31, endo-HI), 2.44 (m, 2 H,H2 orH5), 2.38 (m, 2H, H2 or H5)and2.36 [t, 1 H, J = 8.25 Hz,(b) Compound 5. As in ( a ) but compound 2 (ca.0.07 g) wasdissolved with stirring in Me,CH(NO,) (20 an3); reductionin volume and cooling to -20 OC gave a quantitative yield oforange crystals of 5. IR (cm-') 1575, 1151 (NO,); cp and q4-ring); 4.34 (s, 5 H, cp), 3.20 (t, br, 1 H, endo-H'), 2.42 (9, br,2 H, H295) and 0.85 (s, 6 H, Me,CNO,).(c) Interaction of NO and Co(cp), in either neat MeNO,or Me,CH(NO,) gave a quantitative yield of the respectivesalts on work-up; both are unstable when solvent is removed.The characterisation was by IR and NMR spectra.( d ) The reaction of compound 2 and EtNO, was carriedout as in ( a ) but 2 (0.16 g) was dissolved in EtNO, (3 cm3)and EtzO was added to precipitate the yellow salt 6 inquantitative yield (0.1 g). Evaporation of the mother-liquor anddissolution of the residue in toluene gave a quantitative yield(0.1 1 g) of orange Co(cp){q4-C,H,[CH(Me)NOz-exo]} 7.Compound 6: IR (cm-I) 1552, 1260, 1370 and Co(cp),+ bands;'H NMR (CDCI,) 6 5.93 (cp), 3.24 (9, J = 7.26, CH,) and0.62 (t, J = 7.26, CH,), both for EtNO,.Compound 7: IR(cm-') 1543, 1325,1174 plus cp and q4-CsHs bands; 'H NMRor H4), 4.34 (s, 5 H, cp), 3.05 [d of q, I H, J = 6.6 for q, 7.6for d, CH(Me)NO,], 2.85 (d of pseudo-t, 1 H, J = 7.59 ford, 2.64, 2.31 Hz for t), 2.50 and 2.19 (m, 1 H, H2 or H5 of q4ring).CP and q4-C5H5 bands; 1528, 1360 (NOZ);" 'H NMR (C6D6)CH(NO, 13 -C,H5 bands. 'H NMR (C6D6): 6 4.74 (t, br, 2 H, H3*4 of q4(C6D6) 6 4.75 (m, 1 H, H3 or H4 of q4 ring), 4.70 (m, 1 H, H2230 J. CHEM. SOC. DALTON TRANS.1994Table 2 Crystal data and structure refinement for compounds 2 4 , 8 and 9FormulaM*Crystal system?iceblACIA4"PI"rl"u/A3ZDJMg m-3F(oo(9p( Mo-Ka)/mm-'Reflections collectedIndependent reflections (&,)Maximum, minimum absorption correction factorsData, parametersGoodness of fit, F2Final R indices R 1, wR2CI ' 2 m 1(all data)Largest difference peak and hole/e A-32394.22Monoclinic1 1.537(4)10.197(2)13.265(2)9 0 )96.81(2)90)1549.5(7)41.6908082.14150502471 (0.0485)0.775,0.5972465,2880.3830.0320,0.08000.0566,O. 1230CzoHzoCo2OP21la0.376, - 0.5 1 13C1,H,*CoNO,267.17Monoclinicp21 la7.520( 1)17.904(4)8.433( 1)W O )108.13(2)90(0)1079.0(3)41.6455521.53754732774 (0.0664)1.293, 1.0592756,2010.41 70.0392,0.07470.0848,O.13340.552, -0.5394cz lH2 1Co2NO2437.25TriclinicPT5.615(1)I 1.920(2)13.583(3)104.05( 1)94.42( 1)91.12( 1)878.6(3)21.6534481.90327692440 (0.0487)0.834,0.5732428,3100.3370.0356,0.08630.0505,O. 15920.334, -0.3908C16H16CON28 1.23TriclinicPT5.756(9)9.43(2)12.23(2)98.7(1)88.7( 1)106.26(8)629.8(2)21.4832921.34120961689 (0.0651)1687,2270.3820.0403,0.09450.0698,O. 1538-0.543, -0.2389Cz2H2oCoN357.32TriclinicPT8.036(8)1 1.060(3)1 1.363(2)118.97(6)1 08.94(4)88.34(4)82 5.6(9)21.4373721.04029622284 (0.0329)2284,2970.3810.0348,0.08840.0406,0.0996-0.395, - 0.266Goodness of fit, S = Fw(F2 - Fc2)2/(n - p)]* where n = number of reflections and p = total number of parameters; R1 = ZIFo - Fc[/cFo;wR2 = pw(F2 - Fc2)2/cw(Fo2)2]* where w = I/[O~(F,)~ + (xP)~] with x = 0 for compound 2 and 0.1 for 3, 4, 8 and 9 and P = [max(Fo2,0) + 2Fc2]/3.Reactions of Compound 2 with Other Substrates.-Allreactions were performed in the same manner fromcompound 2 prepared in situ: NO was passed slowly througha stirred toluene solution of CO(CP)~ (0.1 g in ca.20 cm') for5-10 min as previously described. After filtration, therequired amount of purified substrate [corresponding to 90%yield of 2 from CO(C~)~] was added at room temperature. Theformation of product was immediate with yields quantitativeaccording to NMR spectroscopy, except in the cases ofadamantan-1-01 (80) and PhCSH (23%).All products werecrystallised from toluene; in the case of carbazole the productprecipitated from the reaction mixture. Proton NMR data, inC6D6 unless otherwise indicated, for new compounds are asfollows.Compound 8: 6 6.3-7.1 (m, 5 H, aromatic), 4.70 (pseudo-t,br, 2 H, J, = 1.98, H3v4), 4.49 (s, 5 H, cp), 4.00 (d of pseudo-t,Jd = 8.59, J, = 1.98and2.64,endo-H1),2.95(q, 2H, J = 1.98,H2v5) and 2.93 (d, br, 1 H, J ca. 8 Hz, NH).Compound 9 (in C6D5CD3): 6 6.8-7.15 (m, lo H, aromatic),4.70 (s, br, 1 H, endo-H'), 4.49 (s, br, 7 H, cp and H3*4) and2.91 (s, br, 2 H, H2,5); at -15 to -65 "C, 6 7.1M.8 (m, 10 H,aromatic), 4.68 (s, br, 1 H, endo-HI), 4.45 (s, 5 H, cp), 4.41 (s,br, 2 H, H3v4) and 2.87 (s, br, 2 H, H295).Co(cp)[q4-C5H5(NHC1 oH7)-exo]: 6 7.4-6.8 (m, 7 H, aro-matic), 4.74 (pseudo-t, 2 H, J 1.98 and 1.65 Hz, H3v4), 4.50 (s,5 H, cp), 4.22 (d pseudo-t, 1 H, Jd = 7.9, J, = 2.31, endo-HI),3.72 (d, br, 1 H, Jd = 7.9, NH), 3.06 (q, 2 H, J = 1.98 betweeninner pairs, 2.31 Hz between outer pairs, H2*5).Co(cp)[q4-C5H5(NEt,)-exo]: 6 4.86 (pseudo-t, 2 H, J =1.98 and 2.65 Hz, H3v4), 4.49 (s, 5 H, cp), 3.74 (pseudo-t, 1 H,J = 2.31 and 1.98, endo-H'), 2.80 (q, 2 H, J = 2.65 betweeninner pairs, 2.31 between outer pairs, H2*5) 2.23 (q, 4 H,J = 7.26, CH,CH,) and 0.92 (t, 6 H, J = 7.26 Hz, CH,CH3).Co(cp)[q4-C5H5(OC,oH15)-exo): 6 4.76 (t, 2 H, J = 1.65,H314), 4.50 (s, 5 H, cp), 4.27 (pseudo-t, 1 H, J = 2.64 and 2.31,endo-H'), 3.05 (q, 2 H, J = 1.65 between inner pairs, 2.31between outer pairs, H2*5), 1.91 (s, br, 3 H, bridgehead H ofadarnantyl), 1.74 (d, 6 H, J = 2.96, adamantyl) and 1.45(pseudo-t, 6 H, J = 2.97 and 3.29 Hz, adamantyl).Data not previously reported for known compounds:C~(cp)[q~-C~H~(OMe)-exo],~' 6 4.75 (t, br, 2 H, H3v4 of q4ring), 4.44 (s, 5 H, cp), 4.05 (t, br, 1 H, endo-HI), 3.06 (9, br,2 H, H2s5) and 2.94 (s, 3 H, OCH,); Co(cp)[q4-C5H5(C=CPh)-exo),lob 6 7.33 (m, 2 H, Ph), 6.83 (m, 3 H, Ph), 5.03 (t, 2 H, J =1.98, H3-4), 4.40 (s, 5 H, cp), 3.66 @seudo-t, 1 H, J = 2.64 and2.31, endo-H') and 2.68 (q,2 H, J = 1.98 Hz, H2p5).With SiPh,H to give Co(cp)(q4-C5H,)."" At 270 MHz:6 5.23 (m, 2 H, H3*4), 4.56 (s, 5 H, cp), 2.64 (d pseudo-t, 1 H,J d = 13.87, Jl = 1.98, endo-H'), 2.40 (9, br, 2 H, H2v5) and2.05 (d pseudo-t, 1 H, Jd = 13.88, J1 = 1.99 Hz, exo-HI). Otherproduct: (Ph,Si),O; 6 7.0-7.7 (m, aromatic H).With MeC0,H (in CDCI,). 6 5.82 (s, cp), 2.1 1 (C0,Me).With C6F50H (in CDCl,).6 5.81 (s, cp). "F (referencedto CFCl,): 6 - 171.0 (m, br, 0-, rn-F) and - 188.4 (m, br, p-F).With carbazole. The red solid was insoluble in C6D, andC6D5CD, but in CDCl, the compound Co(cp)[q4-C5H5-(CCI,)-exo) was formed (Found: C, 74.7; H, 4.8; N, 4.5.C2,H,,CoN requires C, 74.4; H, 5.1; N, 4.0%). FAB massspectrum in 3-nitrobenzyl alcohol: m/z 189, Co(cp), + .Reactions of exo-R Compounds with CHCl, or CDCl, .-Allthe nitro compounds when dissolved in the minimum amount ofchloroform at room temperature were converted quantitativelyinto the nitroalkane and Co(cp)[C5H5(CC1,)-exo] the spectraof which were identical to those of authentic samples."" 'HNMR (CDCl,): 6 5.28 (t, 2 H, J = 1.98, H3 and H4), 4.82 (s,5 H, cp), 3.76 (t, 1 H, J = 2.31, HI) and 3.00 (q, 2 H, J =1.65 between inner pairs, 2.31 Hz between outer pairs, H2and H5).All of the other compounds except Co(cp)(q4-C5H6) reactedsimilarly.Reaction of Ir(mes), and NO.-Nitric oxide was slowlypassed into Ir(mes), (ca.0.15 g) in light petroleum (ca. 30 cm3)until the initial dark brown colour disappeared (ca. 20 min) anda dark green-black precipitate formed. This was collectedrapidly and the IR spectrum showed broad bands at 1097,1022and 802 cm-' . The solid was soluble in MeCN or MeNO, wheJ.CHEM. SOC. DALTON TRANS. 1994 223 1Table 3 Fractional atomic coordinates ( x lo4)Atom XCompound 2CO( 1 ) 4 656(1)CO(2) 1966(1)C(101) 3 311(4)C( 102) 4 598(4)C( 103) 4 862(5)3 914(4)'( C( 105) 3 076(4)C( 107) 4 309(5)C( 108) 5 171(5)C( 109) 6 135(4)C( 110) 5 874(5)C( 106) 4 740( 5)Y Atom X Y z z2 319(1)2 088( 1)3 540(4)3 374(5)2 034(5)1295(5)2 202( 5)3 312(6)2 035(6)1115(5)1835(5)3 195(5)5 907(1)1107(1)4 622(3)4 597(3)4 467(4)4 749(3)5 038(4)7 252(4)7 361(4)7 143(4)6 892(4)6 938(4?C(201)C(202)C(203)C(2WC(205)C(206)C(207)C(208)C(209)C(210)02 7 15(4)1 738(4)794(5)1 264(5)2 469(5)3 079(5)3 157(5)2 027(4)1 272(4)1 902(4)2 607(3)3 068(5)2 074(5)2 666(5)3 747(5)3 796(5)633(5)1725(5)1948(5)982(5)186(5)3 931(3)2 810(3)2 599(4)1975(4)1486(4)1 834(4)748(4)99(4) - 448(4)- 135(4)604(4)3 668(2)Compound 3c o 1 494( 1)C(1) 4 125(6)C(2) 4 103(6)C(3) 2 904(7)C(4) 2 174(6)(25) 2 936(6)C(6) 5 19(7)C(7) 552(6)6 113(1)5 979(3)5 942( 3)5 347(2)5 025(2)5 416(2)7 105(2)7 077(2)2 935(1)4 495(6)2 815(7)2 042(6)3 246(6)4 757(6)3 414(6)1761(6)- 594(6)-1 334(6)- 632(7)4 440( 6)1652(5)1 736(5)2 624(5)-2 178(5)6 477(2)6 136(2)6 524(2)6 357(3)6 930(2)5 701(2)6 886(2)6 320(2)932(5)2 108(6)3 642(6)8 673(6)8 253(5)8 115(4)6 767(4)8 346(4)Compound 4CO( 1 ) 1 926(1)COP? 3 779( 1)O(1) 1964(7)O(2) -1 243(7)N 949(8)C(1) 2 414(8)C(101) 1532(8)C( 102) 1 196(9)C( 103) 3 417(9)C( 104) 4 828(9)C( 105) 3 41 7(9)C( 106) - 778(9)C( 107) - 960(9)1771(1)2 716(1)5 795(3)4 713(3)4 851(3)3 805(4)2 894(4)3 351(4)2 540(5)2 069(4)550(4)1 315(4)3 340(4)4 005( 1)9 364(1)7 036(3)6 892(3)6 926(3)6 818(3)5 838(3)4 882(3)4 442(4)4 809(4)5 440(4)3 603(3)2 964(4)C( 108)C( 109)C(110)C(201)C(202)C(203)C(2WC(205)C(206)C(207)C(208)C(209)C(210)1 130(10)2 588(9)1 444(9)2 175(9)3 562(9)5 895(9)5 848(9)3 459(8)961(11)2 582(10)4 762( 10)4 575( 1 1)2 235(12)1233(5)443w18(4)3 371(4)4 105(4)3 708(4)2 551(4)2 272(4)2 333(5)3 147(5)2 617(5)1 528(5)1 349(5)2 427(3)2 747(4)3 487(4)7 797(3)8 751(3)8 822(3)8 232(3)7 835(3)10 092(4)10 793(4)10 863(4)10 227(4)9 750(4)Compound 8c o 3 842( 1)N 2 739(9)C(1) 2 421(12)C(2) 3 468(13)(33) 5 890( 12)C(4? 6 218(11)C(5) 3 927(13)C(6) 1 060(13)C(7) 1 592(11)7 402( 1)6 499(6)6 708(7)8 261(7)8 477(8)7 019(7)6 025(9)6 545(8)8 114(7)2 370( 1)5 413(4)4 260(5)3 962(5)3 677(5)3 351(5)3 473(6)1225(5)1423(5)4 028( 12)4 981(14)3 119(12)1 505( 11)2 054( 12)805( 1 1)- 1 021(13)- 1 569(11)-344(11)8 706(8)7 482(8)6 144(8)7 055(6)6 952(7)7 470(7)8 114(7)8 238(7)7 726(7)1 112(5)742( 5 )840(5)6 285(5)7 380(5)8 268( 5 )8 083(5)7 oow)6 117(5)Compo und 91 lO(1)- 5 131(3)- 3 260(4)-2 149(4)- 1 116(4)-1 009(4)- 1 970(4)1 441(4)2 594(4)2 825(4)1801(4)976(4)2 351(1)1 304(3)1988(3)1 138(3)391(3)1080(3)2 224(3)3 378(4)2 543(4)3 006(3)4 103(3)4 359(3)4 889( 1)2 794(3)3 832(4)4411(3)3 545(3)2 784(3)3 214(3)7 094(4)6 397(4)5 492(4)5 6 15(4)6 629(4)-6 225(4)- 5 766(4)-6 851(4)- 8 448(4)-8 921(4)- 7 846(4)- 5 614(4)-6 512(4)- 6 996(4)-6 593(4)-5 706(4)-5 225(4)2 047(3)3 495(4)4 233(4)3 564(4)2 144(4)1 384(4)- 194(3)- 688(3)-2 128(3)- 3 067(4)-2 579(4)- 1 139(4)2 230(3)2 828(4)2 280(4)1 120(4)534(4)1064(4)2 133(3)2 715(4)2 109(4)902(4)320(4)938(4)N,O was evolved; evaporation or dilution with Et,O gave nocrystalline product only a solid the 'H NMR spectrum of whichwas identical to that observed previously ' for [Ir(rne~)~]+. 'HNMR (CD,CN): 8 6.73 (s, br, 2 H, aromatic), 2.43 (s, 3 H , p -Me) and 2.19 (s, br, 6 H, o-Me).This green-black productwas also formed using cyclohexane or toluene as solvent.Crystal Structure Determinations of Compounds 2 4 , 8 and9.-The X-ray measurements were made on crystals handledunder standard Schlenk procedures and mounted on glassfibres using silicone oil as both a coating and adhesive medium.The unit-cell and intensity data for crystals 2-4 were obtained at150 K, those for the thermally unstable crystals 8 and 9 at 120 K2232 J. CHEM. SOC. DALTON TRANS.1994using a Delft-Instruments FAST TV area detector diffracto-meter and graphite-monochromated Mo-Ka radiation (h =0.710 69 A) following previously described proced~res.~~Structures 2, 3, 8 and 9 were solved by direct methods whilstthat for compound 4 was derived uia a Patterson solution. Allrefinements were by full-matrix least squares on F2 (SHELX92).25 The data for compounds 2 4 were corrected forabsorption using the program DIFABSt6 adapted for FASTgeometry. 27 The non-hydrogen atoms were refined anisotropi-cally and all of the hydrogen atoms in compounds 2,3,8 and 9were located from the difference map and freely refined. The cprings in all of the compounds were refined without geometricalrestraints. However, in compound 4, whilst most of thehydrogens in the structure were experimentally located from thedifference map, and were freely refined, three hydrogens wereplaced in theoretical positions: H(1) (on the bridging group)was refined as a tertiary hydrogen in the riding mode and with afixed thermal parameter: the cp hydrogens H(207) and H(208)were refined as riding model aromatic C-H with the H atoms onthe external bisector of the C-C-C angles.The crystal data andrefinement details are listed in Table 2, fractional atomiccoordinates in Table 3.Additional material available from the Cambridge Crystallo-graphic Data Centre comprises H-atom coordinates, thermalparameters and remaining bond lengths and angles.AcknowledgementsWe thank Mr. Tye, King’s College, London for mass spectra,Professors W.B. Motherwell and C. W. Rees for discussions,Johnson Matthey plc for a loan of iridium and the SERC(M. B. H.) for provision of X-ray facilities.References1 R. S. Hay-Motherwell, G. Wilkinson, B. Hussain-Bates and M. B.Hursthouse, J. Chem. Soc., Dalton Trans., 1992, 3477.2 F. Bottomley, in Reactions of Coordinated Ligands, ed. P. S.Braterman, Plenum, New York, 1986, vol. 2, ch. 3, sect. 6; F. A.Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th edn.,Wiley, New York, 1988, p. 1311; A. Guttierrez, G. Wilkinson,B. Hussain-Bates and M. B. Hursthouse, Polyhedron, 1990,9,2081.3 R. S. Hay-Motherwell, G. Wilkinson, B. Hussain-Bates and M. B.Hursthouse, Polyhedron, 1993, 12,2009.4 G. Wilkinson, J. Am. Chem.Soc., 1952,74,6146.5 ( a ) F. Bottomley and I. J. B. Lin, J. Chem. Soc., Dalton Trans.,1981,271; F. Bottomley, J. Darkwa and P. S. White, J. Chem. Soc.,Dalton Trans., 1985, 1435; Organometallics, 1985, 4, 691; (b)F. Bottomley, personal communication.6 D. A. Muccigrosso, F. Mares, S. E. Diamond and J. P. Solar, Inorg.Chem., 1983,22,960 and refs. therein; S. Bhaduri, B. F. G. Johnson,A. Pickard, P. R. Raithby, G. M. Sheldrick and C. I. Zuccaro,J. Chem. Soc., Chem. Commun., 1977, 354; S. Bhaduri, I. Bratt,B. F. G. Johnson, A. Khair, J. A. Siege], R. Waller and C. I. Zuccaro,J. Chem. Soc., Dalton Trans., 1981,234.7 G. D. Mendenhall, J. Am. Chem. Soc., 1974, %, 5000.8 L. Kuhn and E. R. Lippincott, J. Am. Chem. Soc., 1956,78, 1820;D. J. Millen, C.N. Polydoropoulis and D. Watson, J. Chem. Soc.,1960,689.9 ( a ) J. E. Sheats, J. Organomet. Chem. Library, 1979, 7, 461; ( b )R. D. W. Kemmitt and D. R. Russell, in Comprehensive Organo-metallic Chemistry, eds. G. Wilkinson, F. G. A. Stone and E. W. Abel,Pergamon, Oxford, 1982, vol. 5, sect. 34.4.4; ( c ) H. Bonnemann,Angew. Chem., Int. Ed. Engl., 1985,24,248.10 ( a ) H. Kojima, S. Takahashi and N. Hagihara, J. Chem. Soc., Chem.Commun., 1973, 230; Tetrahedron Lett., 1973, 1991; ( b ) H. Kojima,S. Takahashi, H. Yamazaki and N. Hagihara, Bull. Chem. Soc. Jpn.,1970,43,2272.1 ( a ) M. L. H. Green, L. Pratt and G. Wilkinson, J. Chem. Soc., 1959,3753; ( b ) G. E. Herberich and J. Schwarzer, Angew. Chem., Int. Ed.Engl., 1970,9,897.2 R. T. Morrison and R. N. Boyd, Organic Chemistry, 4th edn., Allynand Bacon, Boston, 1983.3 See ( a ) K. Lammerstein and B. V. Prasad, J. Am. Chem. Soc., 1993,115, 2348; (6) A. T. Nielsen, in The Chemistry of the Nitro andNitroso Groups, ed. H. Feuer, Interscience, New York, 1969, Part 1;( c ) G. Klebe, K. H. Bohn, M. Marsch and G. Boche, Angew. Chem.,Int. Ed. Engl., 1987,26,78 and refs. therein; ( d ) J. A. Cook, M. G. B.Drew and D. A. Rice, J. Chem. Soc., Dalton Trans., 1975, 1973;B. N. Die1 and H. Hope, Inorg. Chem., 1978, 17, 4448; ( e ) J.Yarwood and W. T. Orville-Thomas, J. Chem. Soc., 1963,5991.14 C. J. Attridge, S. J. Baker and A. W. Parkins, Organomet. Chem.Synth., 1971, 1, 183.15 See M. T. Reetz, T. Knauf, U. Minet and C. Bingel, Angew. Chem.,Int. Ed. Engl., 1988,27, 1373.16 Y. Wakatsuki and H. Yamazaki, Synthesis, 1976,26.17 W. Klaui and C. E. Song, Znorg. Chem., 1989,28,3845.18 H. Bonnemann, M. Radermacher, C. Kruger and H. J. Klaus, Helv.Chim. Acta, 1983,66, 185.19 J. M. Birmingham, D. Seyferth and G. Wilkinson, J. Am. Chem. Soc.,1954,76,4179.20 N. Allinger and E. Eliel, Top. Stereochem., 1971, 6, 19; see alsoA. N. Sobolev, V. K. Belsky, I. P. Romm, N. Yu Chernikova andE. N. Guryanova, Acta Crystallogr., Sect. C., 1985, 41, 967;H. Bock, I. Gobel, C. Nather, Z. Havlas, A. Gavezzotti andG. Filippini, Angew. Chem., Znt. Ed. Engl., 1993,32, 1755.21 J. J. Eisch and R. B. King, Organometallic Syntheses, ed. R. B. King,Academic Press, New York, 1965, vol. 1.22 L. J. Bellamy, The Infrared Spectra of Complex Molecules, Chapmanand Hall, London, 1975.23 (a) M. J. Brooks and N. Jonathan, Spectrochim. Acta, Part A, 1969,25, 187; C. N. R. Rao, ref. 13(b), ch. 2, p. 88; (b) D. Hartley andM. J. Ware, J. Chem. SOC. A, 1969, 138.24 A. A. Danopoulos, G. Wilkinson, B. Hussain-Bates and M. B.Hursthouse, J. Chem. Soc., Dalton Trans., 1991, 1855.25 G. M. Sheldrick, University of Gottingen, 1992.26 N. P. C. Walker and D. Stuart, Acta Crystallogr., Sect. A., 1983,27 A. Karaulov, University of Wales, Cardiff, 1991.39, 158.Received 28th January 1994; Paper 4/00539

ISSN:1477-9226    

DOI:10.1039/DT9940002223

出版商:RSC    

年代:1994

数据来源: RSC