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2108 J.C.S. DaltonAlkyl and Acyl DerivativesLigandsof Nickel(ii) containing Tertiary PhosphineBy Ernest0 Carmona.' Francisco Gonz-lez,' and Manuel L. Poveda, Departamento de Quimica Inorgsnica,Jerry L. Atwood and Robin D. Rogers, Department of Chemistry, University of Alabama, AlabamaFacultad de Quimica, Universidad de Sevilla, Sevilla, Spain35486, U.S.A.The interaction of complexes [NiCI,L,] (L = PMe, or PMe,Ph) with Grignard reagents derived from Me,-PhCCH,CI and Me,SiCH,CI yields thermally stable monoalkyl derivatives of the type [NiR(CI) L,], which, whenL = PMe,, afford upon carbonylation at room temperature and pressure the corresponding acyls [Ni(COR)CI-(PMe,),]. Metathesis reactions with KX give [NiR(X)(PMe,),] and [Ni(COR)X(PMe,),] (X = Br, I, NCS, orNCO), while with TI[C6H6], [Ni(CH,CMe,Ph)(q-C,H,)(PMe,)] and [Ni(COCH,CMe,Ph) (q-C5H6) (PMe,)]can be isolated.The synthesis of [Ni(COCH,CMe,Ph)CI(PMe,Ph),l is also reported. The acyls, [Ni(COR)X-(PMe,),], readily carbonylate solutions of the alkyl complexes, [NiR'(X)( PMe,),], providing under certain conditions[NiR(X) (PMe,),] and [Ni(COR')X(PMe,),] in almost quantitative yields. Structures for the new compoundsare proposed on the basis of i.r. and 'H n.m.r. spectroscopic studies. Those of [Ni(CH,SiMe,)CI(PMe,),] and[Ni(COCH,SiMe,)CI(PMe,),] have been confirmed by single-crystal X-ray determinations. Thus [Ni(CH,-SiMe,)CI(PMe,),] crystallizes in the monoclinic space group Pc with a = 15.41 9(3), b = 6.406(2), c = 18.71 l ( 3 )A, p = 92.02(3)", Z = 4, and R 0.031 based on 1 906 independent observed reflections.The phosphine ligandsare trans [P-Ni-P 164(2)"] in a square-planar arrangement. The complex [Ni(COCH,SiMe,)Cl(PMe,),] belongst o the orthorhombic space group Pbca with a = 12.668(3), b = 21.31 2(4), c = 28.925(4) A, Z = 16, and R 0.049for 1 394 independent observed reflections. The oxygen atom is not co-ordinated to the nickel atom [Ni * 03.121 (4) A].ORGANOMETALLIC compounds of nickel(I1) containing Qmetal-to-carbon bonds and tertiary phosphine ligandshave been known for many years, but interest in thesecomplexes has recently increased because of their valueas promoters in organic synthesis.l The correspondingacyl derivatives are rare, the only known examples beingsquare-planar complexes of the type [Ni(COCH,)X-(PMe3)d, some triethylphosphine derivative^,^ and therecently reported five-co-ordinated cationic species[Ni(COR)L]+ [R = CH,, C,H,, or CH,C,H,; L = tris-(tertiary phosphines and arsines)] .In this paper we report the synthesis and charac-terization of alkyl and acyl derivatives of nickel(I1) ofcomposition NiR(Cl)L, and Ni(COR)ClL, (K = CII,-CMe,Ph or CH2SiMe,; L = PMe, or PMe,Ph), and ofsome cyclopentadienyl and other substitution products.The reactions leading to these complexes are summarizedin Scheme 1 .Analytical and spectroscopic data for newcompounds are given in Tables 1 and 2.RESULTS AND DISCUSSIONAZkyZ Complexes.-The dichlorides [NiCl,L,] (L =PMe, or PMe,Ph) react with 1 mol equivalent of Mg-(CH,CMe,Ph)Cl or Mg(CH2SiMe,)C1 in diethyl ether atlow temperature to give the yellow-orange to dark redcomplexes [NiR(Cl)L,] in ca.GOO/, yield. Addition of antrans - [ Ni R(CL)L21/SCHEME 1 R = CH,CMe,Ph or CH,SiMe,; L = PMe, o r PMe,Ph, unless otherwise stated. (i) K X or NaX (X = Br, I, NCS, orNCO) in thf or Me,CO, 25 "C, 8 h ; (ii) L - PMe,, R = CH,SiMe, or CH,CMe,Ph; L = PNIe,Ph, R = CH,CMe,Ph; CO in lightpetroleum-diethyl ether, 5 min; (iiz) L = PMe,, conditions as in (ii); (v) L = PMe,,R = CH,CMe,Ph; Tl[C,H,] in thf or Me,CO, room temperature, 2 h(iu) L = PMe,, conditions as in (2)1980 2109TABLE 1Analytical and spectroscopic data for the monoalkyl complexes [NiR(X)L,]CompoundAK LCH,SiMe, PMe,PMe,PhCH,CMe,Ph PMe,PMe,PhXc1BrINCSNCO c1BrINCSNCOC1BrINCSNCOc1BrNCSNCO[Ni (CH ,CMe,Ph) (q-C,H 6) ( PMeJ 1r' ColourYellow-orangeRedDark redYellow-greenYellow-orangeOrangeRed-orangeDark redBrownBrownRed-brownRedDark redLight brownRed-brownRed-brownRed-brownRed-brownRed-brownYellow-greenAnalysis (%) aC H Others35.8 8.9 P 18.3(36.0) (:::) (18.6)31.828.1(28.2) (6.8)37.4 7.9 N 4.2(37.1) (8.1) (3.9)A 7(31.8) (77:;)52.1 7.9 P 13.0 (67;;) (13.5)(47.5) (6.6)52.3 7.0 N 3.1(52.5) (6.9) (2.9)64.3 7.3 N 2.950.3(50.6) (8.2)(54.3) v;) (3.0)41.0 6.750.754.9(55.0) (9.5) (4.3)61.6 7.457.061.9(61.6) (6.7) (3.7)65.1 8.2 P 9.1(64.9) (8.1) (9.3)rSelected i.r.data cv(NCS) 2 065vsv(NC0) 2 200vsv(NCS) 2 070vsv(NC0) 2 200vsv(NCs) 2 070vsv(NC0) 2 2OOvsv(NCS) 2 070vsV ( ~ ~ ~ ) 2 PWVS'H N.m.r.dMe-P MeeCorMe-Si CH,8.79 (br s) 9.57 (s) 10.51 (br t) e8.68 (br s) 9.53 (a) 10.28 (br t ) e8.75 ( t ) / 9.63 (s) 10.08 (br t ) e8.91 (br s) 9.65 (s) 10.63 (br s)8.76 (br s) 9.56 (s) 10.47 (br t ) c8.44 (br s) 9.62 (s) 10.43 (br s)8.38 (br s) 9.54 (s) 10.33 (br s)8.29 (t) f 9.56 (s) 10.05 (br t )8.60 (br s) 9.70 (s) 10.59 (br s)8.47 (br s) 9.53 (s) 10.49 (br s)8.63 (br s) 8.09 (s) 8.74 (br s)8.73 (br t) 8.15 (s) 8.91 (br t) u8.92 ( t ) l 8.39 (s) h9.00 (br s) 8.45 (s) 9.29 (br s)8.94 (br s) 8.28 (s) 9.21 (br s)8.50 (br s) 8.32 (s) h8.56 (br s) 8.36 (s) L8.72 (br s) 8.49 (s) 9.26 (br s)8.86 (br s) 8.59 (s) 119.06 (d) t 8.31 (s) 8.71) (d) Ia Calculated values are given in parentheses.a Cryoscopically in benzene. 0 Nujol mulls. d Chemical shift ( 7 ) in benzene. Data a t low and high temperatures (inC,DsCDa) are not shown. e J ( P - H ) 14.8 Hz. fJ(apparent) 3 Hz. v J(P-H) 11 Hz. k Obscured by P-CH, signal. f J(P-H) cu. 10 Hz, 4.84 (s) (v-C,H,).excess of the Grignard reagent reduces the yield byformation of an insoluble material which we have notfurther investigated. Dialkyl derivatives have not beendetected even in the presence of excess of phosphine.The monoalkyl complexes are unstable to oxygen bothin solution and in the solid state, although as crystallinematerials they can be handled in air for short periodsof time without apparent decomposition.Molecular-weight determinations in benzene for some of the com-plexes indicate they are monomeric, and on the basisof the similarities in their physical and spectroscopicproperties the remaining compounds have also beenassumed to be monomeric.Metathesis reactions of the chloro-complexes with KX(see Scheme 1) in dry acetone or tetrahydrofuran (thf) atroom temperature give the remaining complexes inTable 1 in almost quantitative yields. Treatment of theneophyl (pp-dimethylphenethyl) complex (1 1) withT1[C,H5] in thf affords the yellow-green cyclopen tadienylderivative (20).Variable-temperature 1H n.m.r. studies for [NiR(X)L,]complexes show a square-planar structure with transphosphines in solution.Owing to rapid ligand exchange,the spectrum of complex (1) exhibits at 35 "C a broadsinglet at T 8.79 and a broad triplet centred at T 10.51for the methyl-phosphine and the methylene protonsrespectively; the methyl protons of the alkyl groupappear at T 9.57, the intensities of these signals being inTABLE 2Analytical and spectroscopic data for the acyl complexes [Ni(COR)XL,]Compound Analysis (%) ' H N.m.r. dr 1 r-- -3 7 I(21) CH,SiMe, PMe, C1 Red 36.4 7.8 P 16.7 362 v(C0) 165Ovs 8.81 (br s) 9.81 (s) 7.21 (s)(36.5) (;fL:) (17.1) (361)Br Red-brown 32.6 395 v(C0) 1 640vs 8.69 (br s) 9.78 (s) 7.13 (s)(32.5) (7.2)(2%)(453)(23)(24)(25)A IR L X Colour C H Others M b Selected i.r. data c Me-P Me< or Me-Si CH,I Red-brown (ti!) v(C0) 1 645vs 8.61 (br s) 9.95 (s) 7.08 (s)NCS Yellow v(C0) 1 620vs 8.91 (br s) 9.79 (s) 7.43 (s)NCO Yellow v(C0) 1 620vs 8.73 (br s) 9.69 (s) 7.41 (s)(26) CH&Me,Ph PMe, C1 Yellow 50.1 7.4 423 v(C0) 1 635vs e 8.67 (br s) f 8.40 (s) 6.40 (s)(%) v(C0) 1 630vs e 8.99 (br s) 8.60 (s) 6.59 (s) Br Yellow-orange 45.4(452)492 v(C0) 1 640vs 6 7.78 (br s) 8.49 (5) 6.43 (s) I Red 39.5NCO Yellow-orange 53.7 8.9 N 3.8 (??C! u(C0) 1635vs 8.88 (br s) f 8.61 (s) 6.78 (s)(30) PMe,Ph C1 Red 60.3 6.4 v(C0) 1 690vs 8.59 (br s) 8.81 (s) 6.62 (s)352 v(C0) 1 630vs 8 9.09 (d) II 8.41 (s) 6.56 (s) (31) [Ni(COCHpCMe,Ph)(q-C,H,)(PMe,)] Red 63.0v(NCS) 2 070vsv(NC0) 2 200vs(80.1) (7$.\)(45.2) W9p)(61.0) (67:;) 8.7(27)(28)(29)(40.9) (6.2)(54.1) (8.7) (3.9) (414) v(NC0) 2 19Ovs(63.2) (7.5) (8.6) (361)a Calculated values are given in parentheses.b Cryoscopicallyin henzene. c Nujol mulls. d Chemical shifts ( 7 ) in C'H,. Data at low and high temperatures (in C,D,CDaor CDJOCD,) are not shown. 8 KBr disc. J In CH&l,. o J(P-H) cu. 10 Hz, 4.69 (s) (q-CbHb)2110 J.C.S. Daltonthe expected ratio of 18 : 2 : 9. On cooling at 10 “C, themethyl-phosphine resonance becomes a pseudo-trip letwhich is characteristic of H,PP’H’,, spin systems withstrong coupling between the pliosphoriis nuclei. Underthese conditions the methylene protons appear as asharp triplet [J(P-H) 14.5 Hz]. The spectra of similarcompounds prepared in this work display essentially thesame features, although the temperature at which tlicP-Me resonance becomes a virtually coilpled tripletincreases with ligand size, and when X = I the tripletis observed even at 35 “C.Relevant ll-I n.m.r. data forother alkyl complexes are included in Table 1 andrequire no further comment.The i.r. spectra of [NiR(X)T,,] compounds showabsorptions characteristic of the alkyl arid pliospliiiieligands. For the tliiocyanate derivatives there is inaddition c?. sharp band at ca. 2 070 c n - l wliicli can beassigned to v(C-N). The position of tliis band suggestsco-ordination through nitrogen and this assumptioil isalso supported by the similarity between tlic visiblespectra of the cyanate and thiocyanate complexes,which show a single d-d transition at ca. 24 100 c m L .The cyanate complexes have an i.r.absorption at 2 200cm-l attributed to v(C-N) of the terminal NCO ligand.A cyl Complexes.-On bubbling CO through solutions of[NiR(X) (PMe,),] compounds, carbon monoxide absorp-t b n takes place in smooth reactions whic-11 lead to tliccorresponding acyls, [Ni(COR)X(PMe,),J, in almostquantitative yield. The reactions cannot be reversed byheating: prolonged reflux in benzene docs not yield theparent alkyl. Complexes (22)-(25) and (27)- (29) canalso be prepared in good yields by metathesis reactionsin acetone or thf. The acyls are more stable towarclsoxygen and moisture than the corresponding alkyls, 110noticeable decomposition being observed after sliortexposures to the atmosphere (2-3 min). Molecularweight determinations, cryoscopically in benzene, indi-cate the compounds to be monomeric (Table 2).Interaction of CO with a solution of the dimctliyl-phenylphosphine derivative (6) gives only decomposi tionproducts, while when R = CH,CMe,Ph, ( l A ) , the cor-responding acyl [Ni(COCH,CMe,Ph)Cl( YMe,Ph),] , (30),can be isolated. This complex is rather unstable, cle-composing slowly in solution even when kept under aninert atmosphere.To our knowledge it is the the firstacyl of nickel stabilized by a non-chelating phospliineother than PMe, or PEt,. On the other hand, reactionof the chloro-complex (26) with Tl[C,H,] in dry acetoneaffords red crystals of (31). This compound is the firstacyl-cyclopentadienyl derivative of nickel( 11) to bereported.Proton n.m.r.studies for these complexes suggesttrans-square-planar geometries, the main difference withthe spectra of the alkyl derivatives being the low-fieldshift of the methylene protons expected upon carbonyl-ation. Also, co-ordination of an acyl group causes adecrease in the temperature of appearance of tlie P-Mepseudo-triplet. Pertinent 1H 1i.m.r. and i.r. data forthese derivatives are included in Table 2. All the com-plexes show a very strong i.r. absorption at 1 630-1 690cm-l due to v(C-0) of the acyl ligand.Previous work has shown that the insertion of carbonmonoxide into Ni-C bonds occurs via an intermediatefive-co-ordiiinte species containing zl co-ordinated COnioleciile, the proposed mechanism being as in Scheme 2.co16e’ 18e’ 16e‘SCHEME 2Tlius, to account for the formation of the 18-electroncomplex [Ni (COCH,)L] [ BPli,] jL = tris(2-diphenyl~~lios-pliinoetliyl)arnii~e] from tlic reaction of thc parent alkylwitli CO, rupturc of thc Ni-N bond and attack o f CO togii.e an intmnecliate alkyl-carbonyl species has beensuggested.* The reaction of \Ni(CH,CMe,Ph) (q-C,H,)-(Phl~,)], (20), with CO could similarly take place withtlissoc.iation ol pliospliine to give a reactive 16-electronspecies.Proton n.m.r. studies of solutions of complexes(20) and (31) provide no evidence of such a process,addition of free phosphine yielding separate resonancesfor the irtx and co-ordinated ligands. I t is not thereforesurprising tliat we have not been able to isolate complex(31) by action of CO on the alkyl derivative (20).Theacyl can only be prepared by inetatliesis of (26)-(29)with T11 C,H,] (see below).The high tlicrmal stability of the acyls reported seemsto suggest that the equilibrium [NiR(X)L,l + CO[Ni(COR)XL,] lies well to the right. However, underappropriate conditions, the equilibrium can be reversed.Thus the reaction of [Ni(COCH2SiMe,)C1(PMe,),1 with[Ni (CH,CH Me,Ph) Br( PMe,),] gives [Ni(COCH,CMe,Ph)-Br(PMe,),] and [Ni(CH,SiMe,)Cl(Pie,),] in almostquantitative yield (see Experimental section for details).For other systems or under different conditions, anequilibrium is established among the four possible species,as can be inferred from lH n.m.r. studies of the reactionmixtures. For example, the l H n.m.r.spectrum of abcnzene solution of complexes (11) and (21) shows thepresence of compounds ( l ) , ( l l ) , (21), and (26) in theratio cn. G : 1 : 1 : 6. As expected, the cyclopentadienylderivatives (20) and (31) do not participate in exchangeprocesses of this type.Since the above reactions can in some cases take placein almost quantitative yield and under very mild condi-tions, it does not seem unreasonablc to suppose that COexchange between (Ni(COR’)XL,] and [NiR(X)L,]might proceed via a CO bridged binuclear intermediateformed by interaction of the 18-electron five-co-ordinateintermediate [NiR’(CO)XL,] and the alkyl complex[NiR(S)L,]. Further studies on these aspects and onthe potential applications of these derivatives as car-bonylating or decarbonylating agents are in progress.The result of tlie X-ray analyses of [Ni(CH,SiMe,)Cl1980 2111(PMe,),], (l), and [Ni(COCH,SiMe,)Cl(PMe,),], (21), aregiven in Figures 1 and 2.Both compounds exhibit adistorted square-planar arrangement with the predictedtrans-phosphine configuration. The Ni-P bond lengthsaverage 2.206(7) A in (1) and 2.201(3) A in (21), and theNi-C1 lengths are 2.256(10) and 2.300(10) A in (1) and(21) respectively. Both types of bonds are similar tothose found in [Ni(COCH,)Cl(PMe,),] [Ni-P 2.200(2)and Ni-C1 2.265(3) A]. The Ni-C bond lengths in thetwo determinations [1.95(2) A in (1) and 1.84 A in (21)]compare well with literature values.6” It is importantto note that the oxygen of complex (21) is not co-ordinated to the nickel atom [Ni * * 0 3.121(4) A].Therefore] the Ni-C(sp2) distance, although shorter thanC (13)[ b )FIGURE 1 Molecular structure and atom-numbering scheme for[Ni(CH,SiMe3)C1(PMe3),1, (1).The two crystallographicallyindependent molecules are designated a and b( 6 )FIGURE 2 Molccular structure for [Ni(COCH,SiMe,)Cl(PMe,),],(21)the Ni-C(sp3), does not show the marked contractionassociated with the q2-acyl mode of co-ordination.8The crystal structures of (1) and (21) both have twomolecules in the asymmetric unit. The independentmolecules do not differ in any important structural para-meter, as may be seen from Tables 3 and 4 and Figuresl(a) and ( b ) , 2(a) and (b). The unit-cell packing, typicalfor molecular compounds of this type, is illustrated inFigures 3 and 4 for (1) and (21), respectively.EXPERIMENTALMicroanalyses were by Butterworth MicsoanalyticalConsultancy Ltd., Middlesex.Molecular weights weremeasured cryoscopically in benzene under nitrogen.Spectroscopic instruments (Perkin-Elmer) : i.r. model 577 ;1H n.m.r., R 12B2112 J.C.S. DaltonTABLE 3Interatomic distance (A) and angles (") forCNi(CH,SiMe,)Cl(PMe,),], (1)Ni( 1)-C1( 1)Ni( 1)-P( 1)Ni( 1)-P(2)Ni( 1)-C( 1)P(l)--C(5)P(l)-C(6)P(l)--C(7)P(2)-C(8)P(2)-C(9)P( 2)-C( 10)Si( 1)-C( 1)Si(1)-C(2)Si( 1)-C(3)!3( 1)-C(4)C1( 1)-Ni( 1)-P( 1)C1 (1)-Ni( 1)-P(2)C1( 1)-Ni( I)-€( 1)P ( 1) -N i ( 1 ) -P (2)P( 1)-Ni( 1)-C( 1)P(2)-Ni( 1)-C( 1)N1( 1)-P( l)-C(5)Ni( 1)-P( 1)-C(6)Ni( l)-P(l)-c(7)C(5)-P( 1)-C(6)C(6)-P( 1)-C(7)Ni( 1)-P(2)-C(S)Ni( 1)-P(2)<(9)Ni( 1)-P( 2)-C( 10)C ( 8)-P( 2)-C ( 9)C( 8)-P(2)-C( 10)Ni( 1)-C( 1)-Si( 1)C( 1)-Si( 1)-C(2)C( 1)-Si( 1)-C(3)C( 1)-Si( 1)-C(4)C(2)-Si( 1)-C(3)C(5)-P( 1)-c(7)C( 9)-P( 2)-C( 10)C(2)-S!(l)-C(4)C( 3)-S1( 1)-c(4)2.264(3)2.2 13( 3)2.201 (3)1.96( 1)1.78(1)1.85(1)1.84( 1)1.84(1)1.81 ( 1)1.81 (1)1.85(1)1.88(1)1.84( 2)1.88( 1)87.9(1)87.6( 1)1 7 3.5( 4)166.0( 1)91.9(4)94.1(4)1 22.4 ( 5 )108.1 (4)116.9(4)101.2( 6)102.4( 7)103.2( 6)1 15.0( 4)1 1 2 .O( 4)122.1(5)101.4( 6)l02.0(6)101.6(6)1 12.6( 6)108.9(6)112.9(7)113.7(6)107.3 (8)3 04.5(7)109.0( 8)Ni( 2)-C1(2)Ni(2)-P(3)Ni(2)-P(4)Ni(2)-C( 11)P( 3)-C( 16)P ( 3)-C ( 1 7)P( 4)-C(18)P( 4)-C( 20)Si(2)-C( 11)Si(2)-C(12)Si( 2)-C( 13)Si (2)-C( 14)Cl( 2)-Ni( 2)-P( 3)C1( 2)-Ni( 2)-P(4)C1(2)-Ni(2)-C( 11)P( 3)-Ni( 2)-P( 4)P(3)-Ni(2)-C(ll)P(4)-Ni(2)-C(ll)N i (2)-P (3)-C ( 1 5)Ni (2)-P( 3)-C( 1 6)Ni(2)-P(3)-C( 17)C( 15)-P( 3)-C( 16)C(16)-P(3)-C(17)Ni (2)-P( 4) -C ( 1 8)Ni (2)-P (4)-C ( 1 9)Ni(2)-P(4)-C(20)C( 18)-P( 4)-C( 19)C( 18)-P(4)-C(20)Ni(B)-C(ll)-Si(2)C(ll)-Si(2)-C(l2)C(ll)-Si(2)-C( 13)C(ll)-Si(2)-C( 14)C(12)-Si(2)-C(13)C(12)-Si(2)-C(14)C( 13)-Si(2)-C( 14)P(3)-C(WP(4)-C(19)C( 15)-P(3)-c( 17)C( 19)-P( 4)-C( 20)2.249( 3)2.2 1 2( 3)2.1 98( 3)1.94(1)1.83(1)1.82(1)1.83(1)1.81 (2)1.82(2)1.82(2)1.85(1)1.86(1)1.88(1)1.87( 1)87.8( 1)87.3( 1)172.4(3)162.0( 1)93.1(3)1 07.2 ( 4)122.1 (4)117.6(4)1 02.3( 6)104.1(5)101.2(6)11 7.4(5)107.9( 5 )124.9(5)102.7 (7)l02.0(8)98.5(7)1 1 1.5 (6)109.9( 6)1 1 1.4( 5)1 14.2( 5)108.2(7)105.6(7)107.2( 7)94.1(3)All preparations and other operations were carried outunder oxygen-free nitrogen following conventional Schlenktechniques.Solvents were dried and degassed before use.The light petroleum used had b.p. 40-60 "C. The ligandsPMe, and PMe,Ph were prepared according to literaturemethods.[Ni(CH,SiMe,)Cl(PMe,),], (1) .-To a stirred suspension of[NiCI,(PMe,),] (0.30 g, GU. 1.0 mmol) in diethyl ether (25 cm3)at -60 "C was added Mg(CH,SiMe,)Cl (0.6 cm3 of a ca.1.45mol dm-3 diethyl ether solution). The resulting mixtureTABLE 4Interatomic distances (A) and angles (") forNi(1)-Cl(1)Ni( 1)-P( 1)Ni( 1)--P( 2)Ni( 1)-C( 1)P( 1)-C( 6)P( 1)-c (7)P(l)-C(8)PP)-C(9)P(2)-C(lO)P(2)-C(ll)C( 11-w 1 )C( 1)-C(2)C( 2)-Si (?)Si( l)-C,(3)Si( 1)-C(4)Si(1)-C(5)[Ni(COCH,SiMe,)Cl(PMe,),]T (21 j '2.2 94 (4) Ni (2)-C1(2)2.203(4) Ni(2)-P(3)2.1 96 ( 4) Ni ( 2)-P( 4)1.78( 2) Ni(2)-C(lS)1.85(1) P(3)-C( 17)1.78(1) P( 3)-C( 18)1.78(1) P(3)-C( 19)1.79(2) P(4)-C(20)1.76(2) P( 4)-C( 2 1 )1.79(2) P(4)-C(22)1.25(2) C(12)-O(2)1.56(2) C( 12)-C( 13)1 .7 3 ( 1) C( 13)-Ci( 2)1.72(2) Si(2)-C( 14)1.90(2) Si (2)-C( 15)1.82(2) Si(Z)-C(lS)C1( 1)-Ni( 1)-P( 1)Cl(1)-Ni( l)-P( 2)Cl(l)-Ni( 1)-C( 1)P( 1)-Ni( 1)-P(2)P( l)-Nl( 1)-C( 1)P(2)-N1( 1)-C( 1)Ni( 1)-P(1)-C(6)Ni(l)-P(l)-C(7)Ni(l)-P(l)-C(8)C(6)-P(l)-C(7)C(6)-P(l)-C( 8)Ni( 1)-P( 2)-C( 9)Ni(l)-P(2)-C(lO)Ni( 1)-€'(2)-C( 11)C(9)-P(2)-C( 11)Ni(1)-C( 1)--0( 1)Ni( 1)-C( 1)-C(2)C(l)-C(2)-Si(?)C( 2)-Si( 1 )-C( .\)C(2\-Si(lkC(41C( 7)-P(l)-C(8)C(9)-P(2)-C( 10)C(lO)-P(2)-C(ll)O( 1)-C( 1)-C(2)90.5( 1)91.2(2)166.1(6)165.9( 2)90.7(5)91.0(5)1 1 4.6 (5)1 1 1.5( 5)121.3(5)102.4( 7)102.4( 7)102.2(6)114.8(6)12 1.2 (5)1 03.4( 9)102.7 (8)101.7 (9)114( 1)116(1)126(1)107.0(9)110.9(6)130(1)119.1(9)C1( 2)-Ni (2)-P( 3)C1(2)-Ni (2)-P( 4)C1(2)-Ni( 2)-C( 18)P(3)-Ni(Y)-P(4)P(:3)-Ni(2)-C( 12)P(4)-Ni (2)-C( 12)Ni(2)-P(3)-C( 17)Ni ( 2)-P( 3)-C( 1 8 )Ni(2)-P(3)-C( 19)C(17)-P(3)-C(lK)C( 17)-P(3)-C( 1'3)C( 18)-P( 3)-C( 19)Ni(2)-P(4)-C( 20)Ni(2)-P(4)-C( 21)Ni(2)-P(4)-C(22)C( 20)-P( 4)-C( 2 1 )C(2O)-P(4)-C( 22)C (2 1 )-P( 4)-C ( 2 2)Ni( 't)-C( 12)-O( 2)Ni(2)-C( 12)-C( 13)O( 2)-C( 12)-C( 13)C( 12)-C( 13)-Si( 2)C(13)-Si('t)-C(14)C( 131-s1(2)-C( 15)2.307( 3)2.1 99 ( 4)2.206 ( 4)1.89( 1)1.77( 1)1.82(1)1.78(1)1.7 7( 2)1.81(1)1.50(2)1.88(1)1.85( 1)1.84(2)1.81(1)1.20(1)1.82(1)91.2(1)1)1.5( 1)168.6( 5)169.2( 2)89.5 (4)89.9( 4)1 20.1 ( 5)113.7( 5)1 14.0( 5)101.2( 7)102.9( 7)102.7( 7)1 16.7( 5)120.3(5)107.9( 5)102.8( 7)105.2( 8)102.2( 7)125( 1)125( 1)1 15.8( 9)1 1 1 .O( 6)11 1.1(6)llO(1)c(i!j--si(ij-~(5j ii6.0(7j cji3j--si@j-cii~j io3.6(7)C(3)-Si( 1)-C(4) 96(1) C( 14)-Si(2)-C( 15) 107.8(7)C(3)-Si( 1)-C(5) 11 1.4(8) C(14)-Si(2)-C(16) 112.9(7)C(4)-Si(l)-C(5) 103.4(9) C( 1 5)-Si (2)-C( 1 6) 1 10.4( 6)was stirred at this temperature for 30 min, then at 0 "C for2-3 h, and finally for 4 11 at room temperature.The solventwas removed in vacuo and the product dissolved in lightpetroleum (30 cm3). The solution was centrifuged toseparate some insoluble material and the product crystal-lized by removing part of the solvent and cooling at - 30 "C.FIGURE 3 Stereoscopic view of the unit-cell packing for (11980 21 13Recrystallization from light petroleum gave yellow-orangeneedles of the pure product in ca. 60% yield.The complex [Ni(CH,SiMe,)Cl(PMe,Ph),], (6), was pre-pared and purified similarly (orange crystals, yield 60%).[Ni(CH,CMe,Yh)C1(PMe3),], (1 1) .-A diethyl ether solu-tion ca.0.63 mol dm-, in Mg(CH,CMe,Ph)Cl (6.6 cm3) wassyringed onto a diethyl ether suspension (40 cm3) of [NiCl,-(PMe,),] (1.16 g , ca. 4.16 mmol) with stirring a t -60 "C.The mixture was warmed to 25 "C and stirred at this tem-perature for 5-6 h. The volume was then reduced in vucuot o 10-15 cm3. Addition of light petroleum (40 cm3) andcentrifugation afforded a solution which upon cooling a t-30 "C yielded the required product as well formed red-brown crystals in cu. 70% yield. This material is useful forsynthetic purposes. Further purification was achieved byrecrystallization from diethyl ether-light petroleum (1 : 3)a t -30 "C.P- /extracted with light petroleum (20 cm3).Filtration andevaporation to ca. 4 cm3, followed by cooling a t -80 OC,afforded yellow-green crystals of the complex which wasrecrystallized froin light petroleum a t -80 "C to give thepure product in ca. 70-80y0 yield.[Ni(COCH,SiMe,)Cl(PMe,),], (21) .-Carbon monoxide wasbubbled (20 "C, 1 atm) * through a solution of (1) (0.10 g,ca. 0.3 mmol) in benzene (5 cm3) for ca. 5 min. The colourchanged from yellow-orange to red. The solvent wasremoved in vucuo and the product crystallized from lightpetroleum a t 5 "C to afford red crystals in approximatelyquantitative yield.Complexes (22)-(25) were obtained when the correspond-ing alkyls were treated with CO in benzene or diethyl etheror when (21) was stirred in thf or acetone with the corre-sponding KX as in the synthesis of (2) : (22) and (23) asred-brown crystals; (24) and (25) as yellow crystals.FIGURE 4 Unit-cell packing for (21)The complex [Ni(CH,CMe,Ph)Cl(PMe,Ph),], (16), wasprepared and purified similarly, as red-brown crystals in ca.60% yield.[Ni(CH,SiMe,)Br(PMe,),], (2).-Complex (1) (0.33 g,1 mmol) and excess of KBr were stirred in tetrahydrofuran(thf) or acetone (30 cm3) for 8-10 h a t room temperature.The solvent was removed in vucuo and the product crystal-lized from light petroleum as well formed red crystals inalmost quantitative yield.Similar reactions of (1) with theappropriate KX afforded the following complexes : (3) asdark red crystals; (4) as yellow-green crystals; (5) as yellow-orange crystals.From (6) were obtained : (7) as red-orangecrystals; (8) as dark red crystals; (9) and (10) as browncrystals. From (11) were obtained: (12) as red crystals;(13) as dark red crystals; (14) as light brown crystals; (15)as red-brown crystals. From (16) were obtained : (17)-(19) as red-brown crystals.[Ni(CH,CMe,Ph) (q-C5H5) (PMe,)], (20) .-A solution of thechloro-complex (11) (0.10 g, ca. 0.26 mmol) in acetone(30 cm3) was stirred for 20 min with Tl[C,H,] (0.08 g, ca.0.3 mmol) ; during this time the colour changed from red toyellow. The solvent was removed in vucuo and the residue* Throughout this paper: 1 atm = 101 325 Pa.[Ni(COCH,CMe,Ph)Cl(PMe,),], (26) .-A solution of thechloro-complex (1 1) (0.38 g, ca.1 mmol) in diethyl ether-lightpetroleum (1 : 1) (20 cm3) was treated with CO (20 "C, 1atm) for 10-15 s after which time a yellow microcrystallinecompound precipitated. The solid was filtered off and re-crystallized from diethyl ether-acetone to afford yellowcrystals in approximately quantitative yield. The follow-ing compounds were obtaiped similarly or by metathesisreactions of (26) in thf or acetone: (27) as yellow-orangecrystals; (28) as red crystals; (29) as yellow-orangecrystals.[Ni(COCH,CMe,Ph)Cl( PMe,Ph),], (30) .-Carbon mon-oxide was bubbled through a solution of (16) (0.20 g, ca.0.38 mmol) in light petroleum (30 cm3) for 5 min. The redprecipitate which formed was shown by lH n.m.r.spectro-scopy to contain a co-ordinated acyl group. Treatment withCO was continued for another 5 min. The solvent wasremoved in vucuo and the complex crystallized from diethylether-light petroleum as red crystals. Recrystallization ofthis material must be carried out quickly to avoid de-composition.[Ni(COCH,CMe,Ph) (7)-C,H,) (PMe,)], (31) .-A proceduresimilar to that followed for the synthesis of (20) affords re2114 J.C.S. DaltonTABLE 5Final fractional co-ordinates for[Ni(CH,SiMe,)CI (€'Me,),], ( 1)-0.1340.5420.47 70.6820.5880.6670.6960.6840.6040.4720.5630.4650.1880.1840.2360.3620.290xla0.00 00.406 4( 1)0.075 7(2)0.301 4(2)0.083 8(2)0.315 9(2)0.468 8(3)0.827 7(2)0.571 O(2)-0.054 2(2)- 0.074 O(7)- 0.260( 2)-0.215( 1)-0.151 O(9)0.102( 1)0.065 l(9)-0.194 O(7)-0.113 3(8)-0.127 2(8)0.029 6(8)0.503 O(6)0.634 3(9)0.649 6(9)0.508 2(8)0.346 3(8)0.266 8(8)0.484( 1 )0.398( I )0.570(1)0.223 4(7)- 0.035- 0.049-0.272- 0.165- 0.2330.243-0.324- 0.268- 0.104-0.2130.1300.0490.0060.1100.2200.1910.2340.1240.1550.048-0.170-0.135-0.0710.0650.0720.003-0.190- 0.105Y lb0.592 7(2)0.371 8(6)0.492 6(5)0.051 7(5)-0.096 5(2)-0.330 2(5)0.730 7(5)0.612 2(6)- 0.054 4(5)- 0.196 9(6)0.756(2)0.73 l ( 2 )0.624(3)0.574( 2)0.532 (2)0.596(2)0.211(2)0.547 ( 2)0.823 ( 2)0.952(2)0.077(2)0.143(2)- 0.241 (3)-0.205(2)0.149( 2)0.27 9 ( 2 )-0.114(2)- 0.124(2)--0.474(2)- o.onl(:l)0.4900.8490.65:)0.7370.8910.5690.5650.7960.3210.2780.2340.7350.4800.5250.5200.76 10.5610.1150.2290.1370.4740.6530.4330.9480.6910.8740.9071.0910.9910.1070.2330.2410.2500.056-0.202- 0.308- 0.355-0.345- 0.252-0.1100.0130.2300.2520.4070.319ZlC0.072 H(2)0.000 00.250 43(8)0.271 2(2)0.096 2(2)0.171 6(2)0.351 8(2)0.158 7(2)- 0 087 O(2)-0.OlfG 7(2)-0.065 6(8)-0.182 4(8)-0.033 0(9)- 0.120( 1)-0.177 l ( 7 )- 0.096 6(8)- 0.068 O(7)0.152 4(7)0.091 9(7)0.224 l(5)-0.203 5(7)0.088 7(7)0.220 4(6)0.320 O(6)0.102 2(6)0.365 8 ( 8 )0.423 O(8)0.158 l ( 7 )0.109 5(8)0.389 G(7)- 0.105- 0.056- 0.205-0,221-0.1690.020- 0.04!)-0.O:~l- 0.162-0.142- 0.076-0.185-0.184- 0.218- 0.020- 0.050-0.111- 0.053- 0.153-0 1250.1270.1930.1750.1R.50.1680.2080.0690.0640.1470.2700.1990.1390.0830.0700.2460.1600.2130.1040.0500.0560.2370.1790.2640 1550.086TABLE 5x / a0.4000.2480.3100.2000.4360.4920.5440.3380.3810.4410.6150.5900.569(Continued)Y Ib0.244-0.262-0.143- 0.035- 0.679- 0.502-0.501-0.2120.041-0.178-0.174-0.1130.071zlc0.0870.1250.0590.0820.3440.4220.3410.4220.4340.4650.3560.4450.376crystals of this complex after crystallization from lightpetroleum a t 5 "C.This product was not detected after pro-longed treatment of (20) with CO.Carbon n/lor,oxide Exchange Reactions.-To a solution of[1C'i(COCH,SiMe3)C1(PMe,),l, (21) (62 mg, ca.0.17 nimol), inlight petroleum-diethyl ether ( 1 : 1) (6 cn13) was added[Ni(CH,CMe,Ph)Hr(F'Me3),], ( I 2) (61 mg, ca. 0.14 mmol), in(i cni3 of the same solvent mixture. The solution wasstirred a t room temperature for a few minutes when ayellow solid precipitated. The solid was filtered off,washed with light petroleum (2 cni3), and dried i g z vacuo.I t was shown (i.r. and 'H n.m.r.) to be identical to a puresample of [Ni(COCH,CMe,Ph)Br(Phle3)2], (27). The fil-trate and washing liquids were taken to dryness, and theresidue dissolved in C,H,. The lH n.1n.r. spectrum wasidentical to that of [Ni(CH,SiMe,)CI(PMe,),], ( 1 ) .Weakresonances due to the slight excess of (2 I ) were also observed.Complexes ( 1 1 ) and (21), and (13) and (21), were dis-solved, in an equitnolar ratio, in C61-16 (0.6 em8). The courseof the reaction was followed by lH n.1n.r. spectroscopy, theequilibrium being attained after standing for several hoursa t 35 "C. In both cases the equilibrium favours the form-ation of tlie neophyl-acyl derivatives. Similar studieswere carried out with other couples of complexes. How-ever, the reaction of [Ni(COCH,CMe,Ph) (q-C5H5) (PMe,)],(31), and [Ni(CH,CMe,Ph)CI(PMe,),], ( 1 l ) , did not give[Ni(COCH2CMe,PhlCl(fMe,),l, (26), even when the condi-tions were such as to insolubilize the latter complex, ifformed.X-Ra,y Data Colledion, Stvucture Determination andRefinement f o r [Ni(CH,SiMe,)Cl(PMe,),I, (1) .-Crystal data.C,,H,,ClNiP,Si, M = 333.5, Monoclinic, a = 15.419(3),A3, Z = 4, F(000) =: 712, D, = 1.20 g cm-3, A = 0.710 69A, p(Mo-K,) = 14.0 cin-l, space group Pc.The latticeparameters were determined from a least-squa res refinementof tlie angular settings of 15 reflections (28 > 32") accuratelycentred on an Enraf-Nonius CAD-4 diffractometer.A crystal of dimensions 0.15 x 0.22 x 0.10 mni wassealed in a thin-walled capillary under a nitrogen atmos-phere. Data were collected on the diffractometer withgraphite-crystal monochroinated molybdenum radiation.The diffracted intensities were collected by the w-28 scantechnique in a manner similar to that previously described.lOAll reflections in one independent quadrant of data werenieasured out to 28 6 50"; 1 906 were considered observed! I 2 3 0 ( 1 ) ] .The intensities were corrected for Lorentz andpolarization effects but not for absorption.Full-matrix least-squares refinement was carried out usingthe SHELX computer program library.'l No correctionswere made for extinction. Atomic scattering factors for Ni,h = 6.406(2), c =7 18.711(3) A, (3 = 92.02(3)", U = 1 847.1980 2115TABLE 6Final fractional co-ordinates for[Ni(COCH,SiMe,)Cl( PMe,) 2], (2 1)X l a0.929 5 ( 2 )0.964 5 ( 2 )1.018 9(4)0.823 8(3)0.807 8(5)0.869 O(4)1.056 O(4)0.907 5(5)1.261 O(5)0.808( 1)0.884(2)0.946(2)0.983 (2)0.934(3)0.767(2)1.168(2)I .007(2)1.003(2)0.856(2)0.744( 2)0.698( 2)1.087( 2)1.365(1)1.235(2)1.297(2)0.7 45( 2)0 827(2)1 .066(2)1.023 3(4)1.120(1)1.138(1)0.921 (2)1.191 (2)0.991 (2)0.9641.0240.9841.0580.93s0.8550.9400.9900.7120.7590.7491.1991.1581.1780.9911.0600.9420.9231.0381.0100.8580.8140.9320.7360.7620.6670.6340.6830.7101.0861.1571.3761.3421.4341.3101.1801.2171.8521.3331.3420.959Y Ib0.651 3(1)0.856 2(1)0.743 6(2)0.793 3(2)0.632 5(3)0.678 9(3)0.904 2(3)0.824 5(3)0.454 8(4)0.883 4(3)0.547 9(7)0.944 6(7)0.573(1)0.529(1)0.4 1 6 ( 2)0.399( 1)0.444(1)0.632( 1)0.692 8(9)0.563 2(9)0.698( 1)0.749(1)0.629( 1)0.894( 1)0.852 3(!))0.898 O(!))0.958( 1)0.823(1)0.970( 1)0.935( 1)0.854( 1)0.743( I)0.851( 1)0.854( 1)0.5540.5230.46 10.4080.3860.4130.3540.4320.4570.4880.4060.6%0.6730.58!)0.7330.7000.6830.5570.5680.5240.6520.7260.7190.77!)0.7800.73!10.6420.5970.5990.8360.8140.8570.9340.9200.3700.9510.9930.8030.7810.8410.9702 / cU.672 27(7)0.503 l l ( 8 )0.683 8(2)0.482 8(2)0.609 7(2)0.722 3(2)0.555 9(2)0.442 6(2)0.723 8(3)0.590 l(2)0.651 8(5)0.516 l(4)0.672 8(8)0.706 O(8)0.764(2)0.674(2)0.734 9(7)0.618 8(7)0.567 7(7)0.576 l(7)0.778 7(7)0.704 8(8)0.734 6(8)0.527 5(7)0.546 5(7)0.620 3(7)0.631 2(7)0.562 4(6)0.585 4(7)0.538 8(ti)0.601 9(6)0.434 4(7)0.434 l(6)0.391 1(6)0.7360.6930.7940.7600.7810.6530.6630.6570.70%0.7610.7530.5840.6300.6400.5830.5470.5480.5610.5510.5!)70.7860.7990.7800.6770 72!10.7090.7430.7080.7620.5900.5430.5360.5200.5560.6370.6400.5880.65!10 6090.6540.604TABLE 60.9610.8380.6790.7320.7630.8670.7620.8001.1131.0181.1161.1811.2351.2271.0130.9920.911xla(CoNtinued)Y / b1.0180.9750.9470.9040.9730.8460.8680.8140.7320.7240.7150.8970.8270.8340.8420.9020.844Ic0.5760.5820.5550.5220.5020.6190.6230.5800.4020.4430.4600.4340.4580.4090.3690.3910.392C1, P, Si, and C were taken from Croiner and Waber,12 andthe scattering for Ni corrected for the real and imaginarycomponents of anomalous dispersion using the values ofCromer and Liberman.13 Scattering factors for hydrogenwere from ref.14.The positions of the Ni atoms were deduced from theinspection of a Patterson map, and the subsequent cal-culation of Fourier-difference maps allowed the location ofthe remaining non-hydrogen atoms. Refinement withisotropic temperature factors led t o R = C(IlF,l - IFc[/)/Z\F',,I = 0.074. Conversion into anisotropic thermal para-meters and further refinement gave R =- 0.044. Thehydrogen-atom positions were determined from a difference-Fourier map but their parameters were not refined. Addi-tional cycles of refinement led to final values of R = 0.031and R' = [Xw(lFo\ - IF,()~/ICW(F,)~]~ =I 0.031.Thelargest parameter shifts in the final cycle of refinementswere less than one hundredth of their estimated standarddeviations. A final difference Fourier showed no featuregreater than 0.3 e A-3. The standard deviation of anobservation of unit weight was 1.25. Unit weights wereused a t all stages; no systematic variation of w(lFoI - IF,])2's. IF,,] or (sin O)/A was noted. The final values of the posi-tional parameters are given in Table 5. The observed andcalculated structure-factor amplitudes and thermal para-meters are given in Supplementary Publication No. STJP22811 (24 pp.).*X-Rccy Data Collecfion, Structure Determination, andRefinement fo. [Ni(COCH,SiMe,)C1(PMe3),], (21) .-Crystaldnfa. C1,H,,CINiOPZSi, M = 36 1.5, Orthorlionibic, a =12.668(3), h = 21.312(4), c = 28.925(4) A, U T= 7 809.2 A3,Z = 1 6 , F(000) = 3 072, L), = 1.23 g A == 0.710 69 A,p(Illo-Z<)a = 13.4 c n - l , space group Ybca.The latticeparameters were determined as above based on 15 reflectionslvith 28 > 28".A crystal of dimensions 1.20 x 0.52 x 0.24 mni wassealed in a tliin-walled capillary under a nitrogen atnios-pliere. The data collection procedure was the same as givenabove. All reflections in one independent quadrant out to28 < 36" were measured: 1 394 were considered observed[ I > 3 0 ( 1 ) ] . The intensities were corrected for Lorentzand polarization effects, but not for absorption.The structure was solved by the methods described above.lcefinenient with isotropic temperature factors gave R ==0.096.The employment of anisotropic thermal parametersled to R = 0.070, and addition of the hydrogen atomsfollowed by further refinement gave final values of R =* For details see Notices to Authors No. 7, J.C.S. Dalton, 1979,Index issue2116 J.C.S. Dalton0.049 and R’ = 0.049. The standard deviation of anobservation of unit weight was 1.59. A final differenceFourier showed no feature greater than 0.3 e Hi3. Unitweights were used, and no systematic variation of w( lFol -IFcl) us. lFol or (sin O)/h was observed. The final values ofthe positional parameters are given in Table 6. Theobserved and calculated structure-factor amplitudes andthermal parameters are given in SUP 2281 1.We thank Miss M. Mojarro for the preparation of some ofthe complexes, and Refineria La RAbida for generous gifts ofsolvents. M. L. P. gratefully acknowledges the Ministeriode Universidades e Investigacih of Spain for a researchscholarship, and J. L. A. thanks the U.S. National ScienceFoundation for partial support.[0/225 Received, 7th Febvuavy, 19801REFERENCESP. W. Jolly and G. Wilke, ‘ The Organic Chemistry of Nickel,’Academic Press, New York, 1975, vol. 2; Adv. OrganometallicChem., 1979, 17, 106, 195.a H. F. Klein, Angew. Chem. Internal. Edn., 1973, 12, 402;D. R. Fahey and J. E. Mahan, J . Amer. Chem. Sot., 1977,99,P. Stoppioni, P. Dapporto, and L. Sacconi, Inorg. Chem.,A. H. Norbury, Adv. Inorg. Chem. Radiochem., 1975, 17, 231.G. Huttner, 0. Orama, and V. Bejenke, Chem. Ber., 1976,L. F. Dahl and C. H. Wei, Inorg. Chem., 1963, 2, 713. * E. Carmona-Guzman, G. Wilkinson, R. D. Rogers, W. E.Hunter, M. J . Zaworotko, and J. L. Atwood, J.C.S. Dalton, 1979,1519.s W. Wolfsberger and H. Schmidbaur, Synthetic React. Inorg.Metal-Org. Chem., 1974, 4, 149; M. A. Mathur, W. H. Myers,H. H. Sisler, and G. E. Ryschkewitsch, Inorg. Synth., 1974,15, 128.l o J. Holton, M. F. Lappert, D. G. H. Ballard, R. Pierce, J . L.Atwood, and W. E. Hunter, J.C.S. Dalton, 1979, 45.l1 SHELX, System of Computer Programs for X-Ray StructureDetermination, G. M. Sheldrick, 1976.12 D. T. Cromer and J. T. Waber, Acta Cryst., 1966, 18, 104.D. T. Cromer and D. Liberman, J . Chem. Phys., 1970, 58,la ‘ International Tables for X-Ray Crystallography,’ KynochH. F. Klein and H. H. Karsch, Chem. Ber., 1976, 109, 2524.2501.1978, 17, 718.109, 2533.1891.Press, Birmingham, 1974, vol. 4

ISSN:1477-9226    

DOI:10.1039/DT9800002108

出版商:RSC    

年代:1980

数据来源: RSC