23i4
R.B.K ~ N AND C A.EFRXTY
Truter's cell compared to those of the P42/n cell of Co(tu)aCl, are a = b = 13.524 (5) 8,c = 8.981 ( 5 ) ,& a n d a = b = 13.508 (7) k, c = 9.106 (5) 8,respectively. Upon examination of the data for Co(tu)&l, i t was noted that of the 885 observed reflections 499 were consistent with the diffraction pattern for Ni(tu)&lz (compare with 404 reflections observed for Ni(tu)4Clz by Truters). However, the other 386 reflections t h a t changed the cell represent 43.6y0 of the total number of reflections but account for only 28.6% of the sum of structure amplitudes. Hence, all five compounds appear to be crystalIographically isomorphous if one examines only the hk0 Weissenberg photographs and the oscillation photograph rotating about the symmetry axis. However, the symmetry axis is -0.1 k longer in the Co type of complex. The Co(tu4)Clz structure is thus a representative structure for M n ( t ~ ) ~ C lFe(tu)dClz, %, and Cd(tu)4C12. I t is safe to say t h a t these are all trans octahedral with both metal-chlorine distances equal in length. On the
Inorganic Chemistry other hand, truns-Ni(tu)4Clpcan be viewed as a distortion toward a tetragonal-pyramid configuration. It should be possible with the right combination of sulfur ligands and halogen to form a N i R Z tetragonal pyramid. It is to be noted that tetrakis(thi0acetamide)nickel(I1) chloride is trans octahedral with equal Ni-C1 distances a t 2.44 0.02 A2jand tetrakis(thi0acetamide)nickel(I1) bromide is also trans octahedral but with a long Ni-Br distance of 3.699 0.004 k z 6The structure of tetrakis(dimethylthiourea)nickel(II) bromide is definitely square planar since the bromine is no longer axial and the Si-Br distance is 4.561 f 0.003 kZ7
*
*
Acknowledgment.-This research was supported by National Institutes of Health Grant GM-13985. (25) J. E. O'Connor, R. L. Girling, and E. L. Amma, to be submitted for pubiication. (26) W. A. Spofford, 111, and E. L. Amma, to be submitted for publication. (27) b1. S. Weininger and E. L. Amma. to be submitted for publication.
CONTRIBUTION PROY THE
UNIVERSITY O F
DEPARTMEST OF
CHEMISTRY,
GEORGIA, ATHESS, GEORGIA30601
Complexes of Trivalent Phosphorus Derivatives. XI. Reactions of Cyclopentadienylmanganese Dicarbonyl Nitrosyl Hexafluorophosphate with Various Tertiary Phosphines and Related Ligands' BY R. B. KINCYANDA.EFRATYa
Received Maich 10, 1969 The manganese salt [CjHjMn(C0)2NO][PFs] reacts with various tertiary phosphines and related ligands upon heating in methanol without ultraviolet irradiation to form yellow to orange substitution products [CjHjMn(CO)(NO)L][PFs] (L = (C&)3P, (CsHj)&S, (CsH6)aSb,and ( c & ) ~ P = c C & j but not ( c 6 H ~ ) ~ B ori (C6H50)3P). The ditertiary phosphine cis(CsHs)zPCH=CHP(CsH:,)z reacts with [CjHjMn(CO)zNO][PF6] to form the red-orange bidentate monometallic (chelate) derivative [C6H5Mn(NO)(diphos)] [PFs]. The other ditertiary phosphines (CsHj)zPCHzCHzP(CsHj)z,trans-(C&)d?CH= H I ) 2form monodentate monometallic derivaCHP(C&)z, (C&)&'C=CP(C6H:,)z, and ( C 6 H j ) 2 P C H 2 C ~ C C H 2 P ( C ~may tives of the type [C,H6Mn(C0)(NO)(diphos)] [PFs] and/or bidentate bimetallic (bridging) derivatives of the type [CjHjMn(CO)(i'iO)]P(diphos)[PF6]2depending on the ligand and the reaction conditions. The triteriary phosphine CH3C [CHzP(CsH6)2]3 reacts with [C6HjMn(CO)2NO] [PFs] to form [(CaH5)zMnz(COj(NO)z(triphos)] [PFBIzin which two of the phosphorus atoms are bonded to one manganese atom and the third phosphorus atom is bonded to the other manganese atom. The infrared and proton nmr spectra of the new compounds are discussed.
Introduction Within the past few years reactions of a variety of neutral metal carbonyls with numerous tricovalent phosphorus derivatives have been investigated. However, corresponding reactions of metal carbonyl cations with tricovalent phosphorus derivatives have received relatively little attention. A few reactions of Re(CO)s+ with chelating tertiary phosphines have been reported to give various substitution products. 6 However, no (1) P a r t X: R. B. King, L. W. H o d , and P. N. Kapoor, Inorg. Chem., 8, 1792 (1969). (2) Fellow of the Alfred P. Sloan Foundation, 1967-1969. (3) Postdoctoral Research Associate, 1968-1970. (4) For a review on metal carbonyl derivatives of tertiary phosphines see T. A. Manuel, A d v a n . Organomelal. Chem., 3, 181 (1965). ( 5 ) Il This paper reports the [PFo] with a reactions of the salt [C5H5Xn(C0)zNO] variety of tertiary phosphines and related ligands. These reactions could be effected thermally in contrast to the corresponding reactions of the isoelectronic C5HjMn(C0)3 with tertiary phosphines which require ultraviolet irradiation.8 (6) A. llavison, h1. L. H. Green, and G. Wilkinson, ibid., 3173 (1961). ( 7 ) P. hI. Treichei, K. W. Barnett, and 12. L. Shubkin, J . Ovganomeld. Chem. (Amsterdam), 7, 449 (1967). (8) R. G. Hayter and L. F. Williams, J . 1no1.g. r V z d . Chem., 26, 1977 (1964).
TRIVALENT PHOSPHORUS DERIVATIVES2375
Vol. 8 , No. 11, November 1969
TABLE I NEWCOMPOUNDS PREPARED IN THISWORK Compounda [CaHsMn(CO)(NO)(P(CsHs)a)1 [PFs] [CsHsMn(CO)(NO) (As(C6Ha)a)1 [PFsl [CsHaMn(CO)(NO)(Sb(C6Hs)a)1 [PFsl [CsHaMn(CO)(NO)((CeHs)nPCzCsHs)1 [PFE] [CsHsMn(CO)(NO) (Pf-Pf) 1 [PFoI [CsHaMn(CO)(NO) ]z(Pf-Pf) [PF6lz [CsHaMn(NO) (cPf=Pf)I [PFsI [CsH5Mn(CO)(NO) (tPf=Pf) 1 [PFsl [CsHsMn(CO)(NO) lz(tPf=Pf) [PFslz [CaHaMn(CO)(NO) ( P E P f )1 [PFsI [CaHsMn(CO)(NO)] z ( P E P f ) [PFslz [CbHaMn(CO)(NO) ]z(PfCECPf)[PFala [(CaHs)zMnz(CO)( N 0 ) d t r W o s )1 [PFsIz
Color Orange Orange Pale orange Light yellow Orange Deep yellow Red-orange Deep yellow Yellow Yellow-orange Orange Pale orange Yellow
Mp.’C 180-183 dec 157-160dec 169-170 dec 79-80 165-166 209-210 dec 227-228 dec 192-194 dec 219-221 dec 143-144 213-215dec 203-205 dec 214-215dec
C -Calcd 48.9 45.9 42.7 51.4 53.2 43.7 53 9 53.4 43.7 53.6 43.8 45.0 50.3
Analyses, % ----NFound Calcd 3.3 2.4 3.3 2.2 3.2 2.1 3.6 2.3 4.2 1.9 3.6 2.7 4.5 2.0 3.7 1.9 3.3 2.6 3.5 1.9 2.5 3.2 2.6 4.Zb 2.3
-----H--Found 49.4 46.1 42.8 53.3 53.2 44.0 54.1 53.3 44.1 53.6 44.3 45.5 50.3*
4 For the abbreviations of the ligands used see the Experimental Section. samples.
b
Calcd 3.4 3.2 3.0 3.3 4.1 3.3 3.9 3.8 3.1 3.5 2.9 3.2 4.0
Found 2.3 2.1 2.0 2.1 1.9 2.6 1.8 1.9 2.6
1.9 2.5 2.1
---MnCalcd 9.2 8.7 8.1 9.0 7.6 10.5 7.9 7.6 10.7 7.7 10.5 10.3
Found 9.4 8.7 8.3 8.5 7.5 10.2 7.5 7.9 10.7
8.1 10.8 10.5
Average of analyses on two independently prepared
boiled under reflux for 6 hr. Solvent was removed from the reaction mixture a t -35 mm. The product was extracted from Microanalyses (Table I ) were performed by Pascher Mikrothe residue with several portions of dichloromethane. The analytisches Laboratorium, Bonn, Germany. Tungsten(V1) filtered extracts were treated with benzene and then concentrated oxide was added as a catalyst during the combustions to deterat -35 mm. The product which separated was recrystallized mine carbon and hydrogen. This expedient assured complete from a mixture of dichloromethane and benzene to give 0.52 g oxidation of the carbon to CO2 eliminating the previously ob(27% yield) of pale orange [C6HjMn(CO)(NO)Sb(CsH5)3]served tendencies3 for low carbon analyses in organophosphorus [PFsl. derivatives of transition metals. Melting and decomposition A mixture of 1.5 g (4.27 mmol) of [CEHSM~(CO)QXO][PF~], points were taken of samples in capillaries and are uncorrected. 1.0 g (3.57 mmol) of ( C ~ H ~ ) Z P @ C C ~ and H E , 75 ml cf methan31 A nitrogen atmosphere was always provided for the following was boiled under reflux for 1.5 hr. The methanol was then rethree operations: (a) carrying out reactions, (b) handling all moved a t -35 mm and the dry residue was washed with benzene. filtered solutions of metal complexes, and (c) admitting t o evacuThe product was extracted from this residue with several porated vessels. tions of dichloromethane. Ethanol was added to the filtered Triphenylphosphine and diphenylchlorophosphine were purdichloromethane extracts. Upon concentrating and cooling chased from Eastern Chemical Corp., Pequannock, K. J. Tri0.73 g (%yoyield) of light yellow [C5H6Mn(CO)(NO)(C6Ha)~phenylarsine, triphenylstibine, and triphenylbismuth were P&CC&E] [PFo] was obtained. generous gifts of M and T Chemicals, Inc. The remaining triReaction of [CEH5Mn(CO)2NO] [PFs] with (C6HE)2PCH2CHnPcovalent phosphorus derivatives were prepared by one of the (C~HE)~.-Amixture of 0.44 g (1.25 mmol) of [C5H,Mn(C0)2following two general methods: ( I ) reaction of diphenylchloroNO] [PFG],0.50 g (1.25 mmol) of ( C ~ H S ) Z P C H ~ C H ~ P ( Cand ~HE)~, phosphine with an organolithium or organomagnesium derivative: 100 ml of methanol was boiled under reflux for 1 hr. The reac( C e H S ) 2 P k c C & 1 0and (CBH:,)~PC=CP(C&)Z(PfEPf);” (2) tion mixture was filtered hot to give 0.065 g (10% yield) of deep reaction of lithium diphenylphosphide with an organic halide: [PFs]*. The filtrate was yellow [C,H,Mn(CO)(iYO)],(Pf-Pf) (CsH6)*PCH2CH~P(C~H~)~ (Pf-Pf),12 cis- and tl.ans-(C&)zevaporated to dryness a t -35 mm. The residue was extracted PCH=CHP(CaH5)z (cPf=Pf and tPf=Pf, re~pectively),’~ with several portions of dichloromethane. Treatment of the (C6HE)~PCH2CrCCHzP(CaHs)z(PfCSCPf ),l* and CHaCfiltered dichloromethane extracts with ethanol followed by con[CH~P(C~HE (triphos).lZ )~]~ The salt [CaHEMn(CO)~NO] [PFB] centration at -35 mm gave 0.44 g (497, yield) of orange [CEHEwas prepared by the previously described procedure.16 Mn(CO)(NO)(Pf-Pf ) [PFG] . Reactions of [(CaH6Mn(CO)zNO] [PFe] with Monodentate A similar reaction between 0.806 g (2.30 mmol) of [c,&&fnLigands.-A mixture of 2.0 g (5.7 mmol) of [CsH:Mn(CO)&O](CO)ZISO][PF,] and 0.46 g (1.15 mmol) of (C6H6)2PCH$CH2P[PFe], 1.5 g (5.7 mmol) of triphenylphosphine, and 50 ml of (C6H6)2 gave 0.475 g (40y0 yield) of [C6H;Mn(CO)(NO)]zmethanol was boiled under reflux for 1.5 hr. The reaction mix(Pf--Pf)[PF6]2 and 0.148 g (18% yield) of [CSHjMn(CO)(NO)ture was cooled to room temperature. The resulting orange (Pf-Pf)] [PFB]. precipitate was filtered off, washed with methanol, and then reReaction of [C5HEMn(CO)pNO] [PFB]with C ~ ~ - ( C ~ H ~ ) ~ P C H = crystallized twice from a mixture of methanol and dichloroCHP(C~HS).Z.-Amixture of 2.0 g (5.70 mmol) of [C6HaMn(C0)2methane to give 1.98 g (60% yield) of orange [CsH5Mn(CO)NO] [PF6],2.0 g (5.06 mmol) of C ~ ~ - ( C ~ H ~ ) ~ P C H = C H P ( C ~ H ~ ) ~ , (NO)P(CBH~)II [PFd. and 100 ml of acetone was boiled under reflux for 17.5 hr. SolA similar reaction between [CrH5Mn(C0)&O][PFa] and trivent was then removed from the reaction mixture a t -35 mm. phenylarsine gave a 36% yield of orange [C6HjMn(CO)(NO)AsThe oily residue was washed with several portions of benzene to [~FB]. (CSHS)~] remove unchanged phosphine. The residue was then extracted A mixture of 1.0 g (2.85 of [CjH:Mn(CO)zNO][PFs],2.0 with several portions of boiling methanol. The filtered red solug (5.65 mmol) of triphenylstibine, and 75 ml of methanol was tion was allowed to cool to room temperature and finally concentrated a t -35 mm. The crystals which separated were recrystallized from a mixture of dichloromethane and ethanol to (9) R. B. King, K. H. Pannell, C. A. Eggers, and L. W. Houk, Inoug. Chenz., 7 , 2353 (1968); R. B. King, L. W. Houk, and K. H. Pannell, ibid., 8, give 0.87 g (22% yield) of red-orange [C:HjMn(NO)(cPf=Pf)]1042 (1969). [PFc]. (10) W. Chodkiewicz, P. Cadiot, and A. Willemart, Comfit. Rend., 260, 866 Reaction of [CEHEMn(CO)~NO] [PFe] with ~ ~ Z ~ - ( C ~ H ~ ) ~ P C H = (1960). CHP(CBHE)Z.-A mixture of 2.0 g (5.72 mmol) of [CbHbMn(11) H. Hartmann, C. Beerman, and H. Czempik, Z . AnoYg. Allgem. Chem., 287, 261 (1956). (CO)zNO][PFe], 1.2 g (3.03 mmol) of ~ ~ ~ ~ ~ - ( C B H & P C H = C H P (12) J. Chatt and F. A. Hart, J. Chem. Soc., 1378 (1960). ( C B H ~and ) ~ , 75 ml of methanol was boiled under reflux for 2.0 hr. (13) A. M. Aguiar and D. Daigle, J . A m . Chem. Soc., 86, 2299 (1964). Solvent was then removed from the reaction mixture at -35 mm. (14) R. B. King and A. Efraty, to be submitted for publication. The residue was extracted with several portions of dichloro(15) K. B. King and M. B. Bisnette, Jnorg. Chem., 8 , 791 (1864).
Experimental Section
2376 R. B.KINGAND A. EFRATY
Inorganic Chenaistry
methane. The filtered dichloromethane extracts were evapofailed to react with [CsH5Mn(C0)2NO] [PF6]in boiling rated a t -35 mm and the residue recrystallized from a mixture of methanol using techniques similar to those successfully dichloromethane and benzene to give 0.67 g (17y0yield) of deep employed for the compounds described in this paper. yellow [C,H,Mn(CO)(sO)(tPf=Pf)] [ ~ F G ] . The presence of the hexafluorophosphate anion in all The residue from the original dichloromethane extraction was the binuclear derivative [C~HjMn(Co)(sO)l,(tPf=Pf)[PFs]2. of the new compounds described in this paper was conThis residue was washed with dichloromethane and benzene. firmed by the presence of a strong v(PF) infrared Recrystallization from boiling acetone gave 1.28 g (43% yield) of frequency in the range 800--820 cm-I in their infrared yellow [ CjH&!h( CO)(NO)]z(tPf=Pf) [PFe]2 . spectra. Reaction of [CjHjMn(CO)2NO] [PFs] with (CsHj)2PCrCPThe behavior of the ditertiary phosphines when (CsHj)z.-A mixture of 0.9 g (1.7 mmol) of [CjHjMn(CO)&O][PF6]is particularly treated with [C5HjMn(C0)2KO] [PFG],2.0 g (5.08 “01) of ( C G H ~ ) ~ P & C P ( C ~ H and ~)~ 75, ml of methanol was boiled under reflux for 1.5 hr. Solvent was reinteresting. Ditertiary phosphines can interact with moved at -35 mrn. The residue was extracted with dichlorometal atoms in the following three ways: (1) I n the methane. The filtered dichloromethane extracts mere evapmonodentate mononletallic (Ia) case only one phosorated at -35 mm and the residue was washed with benzene to phine atom of the ditertiary phosphines is bonded to the remove excess ligand. Kecrystallization from methanol or a metal atom with the other one remaining uncomplexed. mixture of methanol and dichloromethane gave 1.23 g (52% yield) of yellow-orange [C,H&In(CO)(XO)(Pf=Pf)] [PFB]. (2) In the bidentate monometallic (Ib) case the diFor the preparation of the binuclear derivative a different ratio tertiary phosphine acts as a chelating agent. This type of reactants was used. h mixture of 1.0 g (2.85 mmol) of [CsHjof behavior is only possible if the two phosphorus atoms Mn(CO)2NOj[PFG],0.46 g (1.17 mmol) of ( C S H ~ ) Z P = C P ( C ~ H ~ ) ~ , are so situated spatially that they can form a ring with and 100 ml of methanol was boiled under reflux for 2 hr. Solvent the metal atom. In the cases of the ditertiary phoswas removed at -35 mm. The residue was extracted with dichloromethane. The filtered dichloromethane extracts were phines used in this study this stereochemical condition is evaporated at -35 mm. The residue was recrystallized from a fulfilled only by the two ligands (C6Hj)2PCH2CH2Pmixture of dichloromethane and ethanol to give 0.025 g (2.170 (C6Hj)2 and cis-(C6Hj)*PCH-CHP(CsHj)2.(3) In yield) of orange [ CjHsMn(CO)(KO)]z(PfzPf)[PFBIP. the bidentate bimetallic (IC) case the ditertiary phosReaction of [CsHjMn(CO)aNO][PFe] with (C6H:)2PcH&= phine acts as a bridge between the two metal atoms. CCH~P(CBH~)~.-A mixture of 0.80 g (2.28 mmol) of [CsHjMnIn the cases of metal carbonyl derivatives, formation 1.05 g (2.50 mmol) of (C6Hj)2PCH2C=CCHnP(CO)zXO][PF,], ( C G H ~and ) ~ , 150 ml of methanol was boiled under reflux for 2.5 of bidentate monometallic (“chelate”) derivatives will hr. The reaction mixture was filtered hot and the filtrate was be hindered by the increased resistance of carbonyl allowed to stand at room temperature for 2 days. The deep groups t o substitution upon replacement of some carorange crystals which separated were purified by crystallization bonyl groups with tertiary phosphine ligands. This from a mixture of dichloromethane and ethanol to give 0.445 g (39% yield) of pale-orange [C,H,;Mn(CO)(n-O)],(PfC~CPf)- arises from the reduced ?r-acceptor ability of tertiary [PFslz. phosphines as compared bvith carbonyl groups, thereby Reaction of [CjH,Mn(C0)2NO][pF6] with CH&[CHnPincreasing the electron density available for retrodative (C6Hj)z]3.~--~kmixture of 2.0 g (5.72 mmol) of [C5HjMn(CO)zR bonding with the fewer remaining carbonyl groups, N O ] [PFG],2.0 g (3.21 mmol) of CH3C[CH2P(C6Hj)2]a, and 100 hence increasing the strength of the metal-carbon 1111of niethaiiol was refluxed for 1.5hr. Solvent was removed at bond. This will increase the tendency for the second -35 mm and the residue was washed with benzene to remove any excess ligand. The dry solid was extracted with dichloromethtricovalent phosphorus atom in a potentially chelating ane. Ethanol was added to the filtered dichloromethane exditertiary phosphine to replace a carbonyl group tracts. Concentration at -35 mm gave a precipitate which was attached to a second metal atom rather than a further purified by recrystallization from a mixture of dichloromethane and ethanol t o give 2.0 g (5676 yield) of yellow [(C5H5)2Mn2- carbonyl group attached to the metal atom to which the first phosphorus atom has bonded. Thus bidentate ICO)(NO)g(triphos)][I’F6I2. I n a repeat experiment a mixture of 1 .O g (2.85 mmol) of [C5H;Mri(C0)2XO][I’Fs] and 0.59 g (0.95 bimetallic (IC) behavior \\-ill be favored over bidentate inmol) of CH~C[CHZI’(C~HG)P]S gave 0.560 g (43% yield) of monometallic behavior (Ib) in metal carbonyl complexes [(CjH:,)2M1i~(CO)(NO)~(triphos)] [PF,], identical with the materelative t o metal halide complexes ; in metal halide rial prepared as described above.
Discussion The reactions of [C5HjMn(C0)2NO] [PFs] with the various ligands discussed in this paper did not require ultraviolet irradiation in contrast to similar reactions of ivith the isoelectronic C j H j M ~ ~ ( C O ) aProducts .S the type [CjHJh(CO)(NO)L] [PF6]were obtained not only with the monodentate ligands but also with the ditertiary phosphines Pf-Pf, tPf=Pf, and PfEPf. The monometallic derivatives of the type [C5H5Mn(CO) (NO)L][PF6] were readily soluble in dichloromethane and thus could be separated from any unchanged [ C S H ~ M ~ ( C O ) ~[PFs] N O ] which is insoluble in dichloromethane. The potential ligarids tripheriylbismuth, triphenyl phosphite, and hexakis(trifluor0methyl)- 1,4-diphosphabicyclo [2.2.2]o c t a t r ien e - 2 5 7 )
)
complexes a potentially chelating ditertiary phosphine always acts as a chelating ligand (Ib) rather than a bridging ligand (IC).
la
Ib
IC
The only ditertiary phosphine used in this study which acted as a chelating agent when allowed to react with [ C S H ~ M ~ ( C O ) ~[PFe] N O ] was cis-(CeH5)2PCH= CHP(C&) which formed red-orange [CjHj;Lln(NO)(cPf=Pf)][PFs] (11). The absence of v(C0) freclueiicies (Table 11) ill tlie infrared spectruiii of I i con(16) For a review of tertiary phosphine complexes of metal halides see G. Booth, Adoan. I I Z O Y EChem. . Radiochem., 6, 1 (1964).
Vol. 8, No. 11, November 1969
TRIVALENT PHOSPHORUS DERIVATIVES 23'77 TABLE I1
INFRARED SPECTRA OF SOMECYCLOPEXTADIENYLMANGANESE NITROSYL DERIVATIVES IN
-_
CompoundC
V(C0)
[C6HsMn(C0)2NOl[PFGI [CsHsMn(CO)(I\;O)(P(C6H5)3)1 [PFd [C~H~M~(CO)(NO)(A~(CGH~)~)] [PFS] [C,HsMn(CO)(No)(Sb(C6Ha)3)1[PFd [C~H~M~(CO)(NO)((C~H~)~PCZCBH~)] [PFs] [ CaH5Mn(CO)(NO)(Pf-Pf)] [PFG] [CaHjMn(CO)(NO)]s(Pf-Pf) [ PFs]2
THE
2200-1700-C~-~R E C I O N = I ~
Infrared spectrum, cm-1 v(NO)
2114,2076 2028 2028 2029 2035 2038
V(C==C)
1865 1787 1788 1789 1798 1808
I::;{
...
... ... ...
9065
...
{;K)
...
... 1770 [CjH5Mn(CO)(NO)(tPf=Pf )] [PF,] 2040 1800 ... 2043 1803 ... [ CsHaMn(CO)(NO)]z(tPf=Pf) [PFG] z [ C,HjMn(CO)(NO)(Pf=Pf)][PFB] 2041 1797 2106 [ CjHjMn(CO)(NO)]Z( P f r P f ) [ PFfilz '2042) 18141 Absent 2020 f \ 1789j 2030 Absent 1803 ... 1790,1742 2022 The infrared spectra a These spectra were taken in potassium bromide pellets on a Perkin-Elmer Model 257 grating spectrometer. of all of these compounds exhibited strong absorptions in the range 860-820 cm-l from the v(PF) of the PFs- anion. For the abbreviations of the ligands used see the Experimental Section.
[ CsHjMn( NO)(cPf=Pf)] [PFG]
/
'I
TABLE I11 PROTON NMRSPECTRA OF SOME CYCLOPENTADIENYLMANGANESE NITROSYL DERIVATIVES~ -Proton
r
C6H5
nmr spectra, CsH3
T
