Electrophilic Attack of Group 11 and 12 Metal Fragments on the

Crystal Structure of the Transversally Bridged Alkyne Complex [W2(.mu. ... η-Alkynyl and Vinylidene Transition Metal Complexes. 8. Synthesis of Bimet...
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Organometallics 1995, 14, 57-62

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Electrophilic Attack of Group 11 and 12 Metal Fragments on the Dinuclear Anions [M2(/l-~C2Ph)(C0)4(~-CsHs)2](M = Mo, W). Crystal Structure of the Transversally Bridged Alkyne Complex [W2(/l-PhCAUPPhs)(CO)Q(@SHS)~I Montserrat Ferrer, Oriol Rossell, and Miquel Seco Departament de Quimica Inorganica, Universitat de Barcelona, Diagonal 647, E-08028Barcelona, Spain

Maria Angela Pellinghelli and Antonio Tiripicchio* Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita di Parma, Centro di Studio per la Strutturistica Difrattometrica del C.N.R.,Viale delle Scienze 78, 1-43100 Parma, Italy Received May 31, 1994@ The dinuclear anions [MZ(~-U:CZP~)(CO)~(~-C~H~)Z](M = Mo, W) react with gold halides CIAuPR3 (R = Ph, Me) in tetrahydrofuran to yield the p-alkyne bonded complexes [Mz(pP~CZAUPR~)(CO)~(~;~-C~H~)ZI [M = Mo, R = Ph (la),R = Me (2a);M = W, R = P h (lb),R = Me (2b)lin good yield. The structure of l b has been determined by X-ray diffraction methods. The crystals are monoclinic, space group P21/c with 2 = 4 in a unit cell of dimensions a = 8.417(4)A, b = 16.386(6)A, c = 25.352(9)A, p = 90.55(2)”. The structure has been solved from diffractometer data by direct and Fourier methods and refined by full-matrix leastsquares on the basis of 3865 observed reflections to R and R, values of 0.0314 and 0.0362, respectively. The complex displays a WzCz tetrahedral core with W-W and the C-C bond distances of 2.958(1) and 1.387(15)A, respectively. The reaction between the dinuclear anions and HgCl2 leads to a new class of pentametallic symmetric mercury derivatives where the mercury atom forms two Hg-C(p-alkyne) bonds bridging two cluster units.

Introduction In the course of the last years, we have been investigating the incorporation of group 11 or 12 metal fragments, such as AuPR3+ or Hg{Mo(C0)3(r-C5H5)}+, in preformed polymetallic anions t o give mixed transition-metal c1usters.l Results concerning group 6 metals involve the unsuccessful synthesis of the molybdenum (or tungsten)-mercury derivatives, M2Hg, from the dinuclear [M2(CO)&- (M = Cr, Mo, W) anion and ClHg{Mo(C0)3(q-C5H5)}because of the cleavage of the M-M bond.2 On the other hand, the reaction between the hydrido anion [Mo2@-H)(u-dppmXCO)sl-and ClAuPPh3 resulted in the formation of [Moz(CO)&-dppm)(~3H)h-AuPPh3)I3 with an in-plane p3-hydride ligand which holds three metal atoms together by means of a four-center-two-electron bond. As a consequence, the Mo-Au separations are only consistent with the existence of weak Mo-Au interactions. Other potentially interesting group 6 precursors for the synthesis of mixed MAu or MzHg clusters are the anionic complexes [M2hAbstract published in Advance ACS Abstracts, November 1,1994. Seco, M. J . Orgunomet. Chem. 1990, (1) (a) Reina, R.; Rossell, 0.; 398,285. (b) Rossell, 0.; Seco, M.; Jones, P. G. Znog. Chem. 1990, 29,348. (c) Ferrer, M.; Reina, R.; Rossell, 0.; Seco, M.; Solans, X. J . Chem. SOC., Dalton Trans. 1991,347. (d) Reina, R.; Rossell, 0.; Seco, M.; Ros, J.; Yafiez, R.; Perales, A. Inorg. Chem. 1991, 30,3973. Seco, M.; Perales, A. J . Orgunomet. Chem. (2) Reina, R.; Rossell, 0.; 1991, 415, 101. (3) Ferrer, M.; Reina, R.; Rossell, 0.;Seco, M.; Alvarez, S.; Ruiz, E.; Pellinghelli, M. A.; Tiripicchio,A. Organometallics 1992, 11, 3753. @

u : C Z P ~ ) ( C O ) ~ ~ - C ~(M H ~=)Mo, Z I - W).4,5 These species are of particular interest because it has been suggested that the negative charge is delocalized between the metal atoms and the P-carbon atom of the acetylenic ligand. Green et ala5proposed the contribution of two canonical forms to the electronic structure of the anionic compound (Scheme 1). Consequently, electrophilic agents can add to the anionic species by interaction either with the P-carbon atom or with the metal atoms. In fact, the reaction of the bimetallic anions with different electrophilic species (H+,Me+,Et+)was reported5to yield, without exception, the side-on bonded p-a:y2-vinylidenes by nucleophilic attack on the P-carbon atom. Interestingly, however, electrophilic attack on the metal centers has never been observed. All these facts prompted us to explore the reactivity of the proton isolobal agents AuL+ (L = PR3, R = Me, Ph) or HgR+ [R = M o ( C O ) ~ ( ~ - C ~ Phl H ~with ), (M = Mo, W) anthese [MZ~-~:CZP~)(CO)*(~-C~H~)~Iions in order to ascertain the nature of the resulting products as well as some aspects of the mechanism involved in this type of process.

Results and Discussion Treatment of the “in situ” generated anionic com(M = Mo, W) pounds L~[M~~-U:C~P~)(CO)~(~-C~H~)Z] (4) Green, M.; Mercer, A. G.; Orpen, A. G. J . Chem. SOC.,Chem. Commun. 1986,567. ( 5 )Froom, S. F. T.; Green, M.; Mercer, R. J.; Nagle, K. R.; Orpen, A. G.; Rodrigues, R. A. J . Chem. SOC.,Dalton Trans. 1991, 3171.

Q276-7333l95/2314-QQ57$Q9.QQlQ0 1995 American Chemical Society

Ferrer et al.

58 Organometallics, Vol. 14, No. 1, 1995

Scheme 2

Scheme 1

0 Ph

oc'**'in

Ph- C -C -Li

with ClAuPR3 (R = Me, Ph) in THF solution at -78 "C afforded the p-alkyne neutral compounds [M2@-PhC2A u P R ~ ) ( C O ) ~ ( ~ ; ~ [M -C~ =H Mo, ~ ) ~R]= Ph (la),R = Me (2a);M = W, R = Ph (lb),R = Me (2b)l in good yield according t o eq 1. C

B

Scheme 3

Equation 1

The reaction was monitored by IR spectroscopy and no changes were observed after the quick formation of the p-alkyne compounds. No intermediate products were detected. Compounds la,b and 2a,b were characterized by elemental analyses and spectroscopic methods. The IR spectra of either THF or toluene solutions showed an identical pattern in the v(C0) region for the four compounds, in agreement with previous data on molecules of this type.6 In all, low-frequency absorptions indicated for the presence of a semibridging CO ligand. However, lH NMR spectra recorded at 25 "C only showed one signal attributable to Cp rings that splits in two different signals on cooling of the solutions to -80 "C, indicating that these complexes undergo a fluxionality process. Accordingly, 13C NMR spectra at room temperature showed only two peaks corresponding to the four inequivalent CO ligands. This fluxionality process prevented the observation of the quaternary carbons of the acetylenic ligands.' The FAB mass spectra were recorded using nitrobenzilic alcohol (NBA) as the matrix and the patterns in all these spectra are very similar. They showed the parent molecular ion and several fragments that correspond to subsequent losses of carbonyl ligands. In the case of PMe3 derivatives (2a,b),Au(PMe3)+ and Au(PMe&+ fragments are the most abundant. The formation of the p-alkyne neutral compounds la,b and 2a,b from the lithium salt of [Mn@-a:CzPh)(C0)4(rpC~H5)21and the corresponding gold derivative is not yet clearly understood. According to the literature5 (Scheme 21, the Mo2 p-acetylide anionic species [ M O ~ @ - U : C ~ P ~ ) ( C ~ ) ~ ((A) ~-C reacts ~ H ~with ) ~ I -proton sources to give a dark blue solution, which on lowtemperature crystallization affords a high yield of the relatively unstable "side-on"bonded vinylidene complex [Moz{p-o:C=CH(Ph)}(C0)4(r-CsHs)zl (B). This dark blue complex is thermally unstable, rearranging in solution at room temperature (10 h) to the red p-alkyne (C).This uncomplex [MO~@-P~C~H)(CO)~(~-C~H~)~] usual rearrangement reaction of a "side-on" bonded (6)Winter, M. J. Ado. Organomet. Chem. 1989, 29, 101 and references therein. (7) Akita, M.; Sugimoto, S.; Takabuchi, A,; Tanaka, M.; Moro-oka, Y. Organometallics 1993, 12, 2925.

vinylidene into a p-alkyne involves an apparent 1,2hydrogen shift from the p- t o the a-carbon. In our case, the reaction of the electrophilic agent AuPR3+ instead of the isolobal H+with the same Moz (or W2) p-acetylide anions seems t o proceed through a mechanism involving the previous rearrangement of the p-acetylide into the p-alkyne lithium complexes [M2@PhC2Li)(C0)4(1;7-C5H5)21and subsequent substitution of the lithium by the AuPPR3+ fragment. The presence of these species in solution has been already postulated5 to explain the mechanism of the deprotonation process of the corresponding p-alkyne complexes which yields, through the less thermodynamicallystable transversally bridged lithium intermediate, the anionic p-acetylide compounds (Scheme 3). Otherwise, the initial attack at the P-carbon by the gold reagent would be followed by an improbable 1,2-diphenyl or AuPPR3+ shift from the p- to the a-carbon atom. Moreover, no observation of a dark blue intermediate in the course of any of the reactions carried out may confirm the suggested mechanism which, on other hand, has been also considered in the protonation of the closely related adducts obtained from CH2=C(Me)C=CLi and [ M ~ ( C O ) ~ ( T ~ C ~ H & I . ~ The molecular structure of lb, confirmed by an X-ray crystal study, is shown in Figure 1 together with the atomic numbering scheme. Selected bond distances and angles are given in Table 1. The acetylenic part of lb coordinates perpendicularly to the ditungsten center to form the dimetallatetrahedral core. The C-C, 1.387(15) A) distance is lengthened by ca. 0.22 compared to that in P ~ C W A U P P At ~ ~the . ~ same time, this distance is a bit longer than the ones found in analogous compounds with a tetrahedral C2M2 core, such as [COZ(CO)s@-FpC=CH)I,1°[Ni2@-FpC=CH)(17-C5H5)21,11or [Mo2(CO)4(17-C5H5)2C-FpC=CH)l7 [Fp = Fe(COMCsH5)1, (8)Froom, S. F. T.; Green, M.; Mercer, R. J.; Nagle, K. R.; Orpen, A. G.; Schwiegk, S. J. Chem. SOC.,Chem. Commun. 1986,1666. (9) Bruce, M. I.; Du@, D. N. Aust. J. Chem. 1986,39,1697. (10)Akita, M.; Terada, M.; Moro-oka, Y. Organometallics 1992,11, 1825.

(11)Akita, M.;Terada, M.; Moro-oka, Y. Organometallics 1992,11, 3468.

Crystal Structure of T w ~ ~ - P h C 2 A u P P h j 3 ( C O ) ~ l l - C ~ ~ ~

Organometallics, Vol. 14, No. 1, 1995 59

$(C-C) = 1.33(3)A, and also a semibrid 'ng carbonyl [W(l)-C = 1.91(3)and W(2)-C = 2.97(3) ,W(1)-C-0 = 173(2)"1. Since ClAuPR3 species reacted cleanly with the anionic dimers, the reaction with digold derivatives (ClAu)z+-PP) (PP = dppm, dppe) was next investigated. This type of compounds allows the syntheses of compounds in which two clusters units are linked by the chelating ligand. l3 Moreover, condensation processes are likely to occur, leading to the formation of new polymetallic clusters of higher nuclearity than their precursors. When (ClAu)zdppmwas added to an "in situ" gener(M ated THF solution of Li[Mz~-a:CzPh)(CO)4(~-C~H~)zl = Mo, W) in a 1:2 ratio at -78 "C in the presence of TlBF4, the compounds [+-dppm){Mz+-AuCzPh)(C0)4( ~ - C ~ H ~ )[M Z)Z = IMo (3a),M = W (3b)Iwere isolated along with other products that did not contain phosphorus that were not fully characterized (eq 2).

f

2 [M2(~o:C2Ph)(CO),(rl-CJHs)2]. + (CIAu)2(pi-dppm)+ 2 TIBF,

thf

1

-78T

O(4)

Figure 1. ORTEP view of the molecular structure of the complex [ W Z ~ - P ~ C ~ A U P P ~ ~ ) ( C(lb) O )together ~(~-C~H~)~~ with the atomic numbering scheme. The thermal ellipsoids are drawn at the 30% probability level. Table 1. Selected Bond Distances (A) and Angles (deg) for

Compound 1M

Au-P Au-C( 15) W( 1)-W(2) W(1)-CE(1) W(l)-C(l) W(l)-C(2) W(l)-C(15) W(l)-C(16) W(2)-CE(2) w(2)-c(3)

2.273(3) 1.998(10) 2.958(1) 2.01 l(13) 1.935(13) 1.955(13) 2.231(11) 2.237(11) 2.010(15) 1.913(11)

wm-c(4) W(2)-C(15) W(2)-C(16) C(1)-0(1) C(2)-0(2) C(3)-0(3) C(4)-0(4) C(15)-C(16) C(16)-C(17)

1.960(12) 2.226(10) 2.148(11) 1.167(16) 1.155(17) 1.202(14) 1.155(15) 1.387(15) 1.459(16)

M=Mo (3a) M = W (3b) Equation 2

Compounds 3a and 3b were isolated as red solids and characterized by elemental analyses and spectroscopic methods. The IR spectra are consistent with the proposed structure since the v(C0) pattern is very similar to that previously observed for compounds 1 and 2. Their lH N M R spectra showed the signals assignable to CHZ protons in the dppm ligand. The 13C NMR P-Au-C(15) 175.6(3) CE(2)-W(2)-C(4) 111.1(6) CE(l)-W(l)-W(2) 121.4(4) W(l)-W(2)-C(3) 88.6(3) spectrum of 3a was not recorded due to the low CE(1)-W(1)-C(1) 111.4(5) W(l)-W(2)-C(4) 66.2(4) solubility of the compound in common deuterated CE(l)-W(l)-C(2) 122.0(5) C(3)-W(2)-C(4) 93.7(5) solvents. Surprisingly, the use of (ClAu)zdppe did not W(2)-W(l)-C(l) 123.6(4) W(l)-C(l)-O(l) 178.1(11) yield any characterizable product even when the workup W(2)'W(l)-C(2) 85.9(4) W(l)-C(2)-0(2) 177.2(12) C( 1)-W( 1)-C(2) 82.4(5) W(2)-C(3)-0(3) 175.9(9) of the reaction mixture was performed at temperatures CE(2)-W(2)-W(l) 152.0(4) W(2)-C(4)-0(4) 169.6(11) below 0 "C. As could be inferred from 31P NMR VT CE(2)-W(2)-C(3) 119.2(5) studies, complicated reactions took place that are now CE(1) and CE(2) are the centroids of the C(5)-C(9) and C(lO)-C(14) under investigation. cyclopentadienyl rings, respectively. Reactivity Studies of [M2(lr-PhC&uPPhs)(COh(q-C&j)21 (M = Mo, W) Since complexes of the type that have been prepared very recently by direct interac[MZ+-RCZR')(CO)~(~~-C~H~)Z] (R, R = organic fragments) tion of the substituted iron acetylene with the corhave been proved to be very reactive toward a great responding metal dimer. The distances Au-C, 1.998variety of substrates, it was of interest to investigate (10) A, and Au-P, 2.273(3) A,are within the range of the variations of this reactivity produced by the substisimilar compounds. The semibridging carbonyl group tution of an organic fragment by a transition-metal is found in the W(2)-C(4)-0(4) unit. The nonlinearity fragment. of the unit 169.6(11)" and the closeness of the W(1)Thus, reactions of sequential linking of alkynes were C(4) contact distance 2.814(11) A are both consistent tested, by treating toluene solutions of [Mz+-PhCzwith an incipient bond formation taking place between A u P P ~ ~ ) ( C O ) ~ ( ~ ~(M - C=~Mo, H ~ W) ) ~ Iwith an excess of W(1) and C(4). The structure of l b is comparable to PhCWPh at 60 "C for several hours. The reactions that of the complex [WZ+-CZHZ)(CO)~(~~-C~H~)ZI, the were monitored by IR spectroscopy and no changes were unique tungsten compound of this type the X-ray observed after a reaction time of 24 h. In a different structure12 of which showed d(W-W) = 2.958(1) A, experiment, la,b were treated with an excess of the activated acetylene Me02CCWCOzMe under the same (12) Ginley, D. S.; Bock, C. R.; Wrighton, M. S.; Fischer, B.;Tipton,

D.L.;Bau, R.J. Organomet. Chem. 1978,157, 41.

(13)Salter, I. D. Adv. Organomet. Chem. 1989,29,249.

Ferrer et al.

60 Organometallics, Vol. 14, No. 1, 1995 conditions. Neither insertion nor substitution of the acetylene were detected. Since strong acids (HC1, HBF4, CF3COOH)react with [M2Cu-RCCR)(CO)4(11-C5H5)21 adducts to yield the corresponding addition products (eq 3),14a toluene solution

X

CF3COO

-

Equation 3

of CF3COOH was added dropwise to an equimolar dissolved amount of [M2G-PhC2AUPPh3)(CO)4(11-C5H5)21 in the same solvent. An immediate change of color was observed. The IR spectrum of the toluene solution revealed the formation of [M2Cu-PhCCH)(C0)4(11-CsH5)21. This process can be understood in terms of the cleavage of the Au-C bond and subsequent formation of the C-H bond. These observations are in agreement with previous results reported by Stone15 and Curtis14 for compounds containing C-Si and C-Sn bonds, respectively. In another experiment, the reaction was repeated with a weaker acid. Solid NH4PF6 was added to a toluene solution of lb. The reaction was monitored by IR. A reaction time of 3 h was necessary for total conversion of [W2@-PhC2AupPh3)(CO)4(r-C5H5)21 to [W2OL-PhCCH)(C0)4(1;1-CgH5)21. In spite of the weaker acid used, the cleavage of the C-Au bond took place and no addition products were obtained. In a further experiment, a toluene solution of l a was irradiated with a medium-pressure mercury lamp with the object of promoting decarbonylation processes that could provoke the formation of new metal-metal bonds. The results, however, were quite different from that expected. After 2 h of irradiation, decomposition products that did not contain carbonyl ligands were isolated. The observed behavior of the alkyne dimers toward irradiation is in agreement with the recently reported photochemical decarbonylation of the adducts [MozbFpCCH)(CO)4(11-C5H5)21that leads to the formation of p3-vinylidenyl derivatives through the generation of an unsaturation on the iron center due to the photoinduced loss of a carbonyl ligands7 In order t o extend the synthetic method to other transition-metal fragments, the reactions of the bimetallic anions with RHgCl compounds [R = Mo(CO)3(qC5H5) and Phl were examined. When the molar ratio between both reagents was 1:1, two different symmetrical mercury species were identified, HgR2 and [Hg(M2@-CCPh)(C0)4(~p25H5)2}21,as a result of a ligand redistribution process (eq 4) that took place even when the reaction mixture was kept at -78 "C. This behavior is quite unusual due to the well-documented16stability of unsymmetrical mercury derivatives of the type RHgR (R, R = organic fragments). However, compounds 4a,b are the first reported examples of Hg-CG-alkyne)bonds. (14)Gerlach, R.F.;D u e , D. N.; Curtis, M.D. Organometallics 1983, 2, 1172.

(15)Beck, J. A.;Knox, S. A. R.; Stansfield, R. F. D.;Stone, F. G. A.; Winter, M. J.;Woodward, P. J . Chem. Soc., Dalton. Trans. 1982,195. (16)Roberts, D.A.;GeofFroy, G. L.In Comprehensive Organometallic Chemistry; Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds.; Pergamon: Oxford, 1982.

Equation 4

In the case of R = M o ( C O ) ~ ( T ~ Cthe ~ Hinstability ~), of the asymmetric derivatives is in agreement with our previous observations on analogous compounds of the type [(q425H5)(OC)3M-HgRl(R = alkyl or aryl groups, M = Mo, W1.l' The reaction of HgCl2 with the bimetallic anion in a 1:2 ratio, in THF solution a t -78 "C, yielded [Hg{M2Oc-CCPh)(CO)4(11-C5H5)2}21 [M = Mo (4a),M = W (4b)I in nearly quantitative yield. The reaction was monitored by IR and no further changes were observed after the formation of the p-alkyne products a t -78 "C. Compounds 4a,b were characterized by elemental analyses and spectroscopically. Their IR and NMR spectra are consistent with the proposed formulation. Elemental analysis and the observation of the M+ in the FABS mass spectra confirmed unequivocally the nature of the products. All attempts to synthesize asymmetric species from 4a,b by adding HgClz in a 1:l molar ratio were unsuccessful. It is well-known that the Pt(PPh3)z fragment inserts into Hg-C bonds, leading to the formation of Hg-Pt bonds.18 The presence of two Hg-C@-alkyne) bonds prompted us to investigate the possibility of insertion of platinum fragments in the new Hg-C bonds with the aim of increasing the metallic nuclearity. The reaction between 4a,b and [Pt(PPh3)2(C2H4)1was carried out in toluene at 60 "C and monitored by IR and 31PNMR spectroscopy. After several hours, IR v(C0) bands characteristic of 4a,b as well as the phosphorus signal corresponding to the platinum derivative remained unaltered.

Experimental Section All manipulations were performed under an atmosphere of prepurified Nz using standard Schlenk techniques. All solvents were distilled from appropriate drying agents. Elemental analyses of C and H were carried out at the Institut de Bioorghnica de Barcelona. Infrared spectra were measured using a FTIR 520 Nicolet spectrometer. 31P{1H} N M R spectra were recorded on a Bruker WF' 80SY instrument (6(85% = 0.0 ppm). 'H and 13C NMR were recorded on a Varian XL-200instrument operating at 200 and 50 MHz, respectively, for lH and 13C (6(TMS) = 0.00 ppm). Fast atom bombardment (FAB) mass spectra were recorded on an Auto SPEC U, Cs+, 30 kV mass spectrometeremploying a 3-nitrobenzyl alcohol matrix (NBA). (17)Rossell, 0.; Seco, M.; Braunstein, P. J . Organomet. Chem. 1984, 273, 233. (18)(a) Sokolov, V.I.; Reutov, 0. A. Coordination Chem. Rev. 1978, 27, 89 and references therein. (b) Braunstein, P.; Rossell, 0.; Seco, M.; Torra,I.; Solans, X.; Miravitlles, C. Organometallics 1986,5,1113.

Organometallics, Vol. 14,No. 1, 1995 61 Table 2. Summary of CrystallographicData for Complex l b mol formula mol wt cryst syst space group

C4oH3oAuOPWz 1170.32 monoclinic P21lc 8.417(4) 16.386(6) 25.352(9) 90.55(2)

V , A3 Z Dcdcdr

g

3496(2) 4 2.223 2176 108.36 0.0314 0.0362

Table 3. Atomic Coordinates ( ~ 1 0 4 and ) Isotropic Thermal Parameters (Azx lo4) with wd's in Parentheses for the Non-Hydrogen Atoms of Compound l b atom

xla

3514.3(5) F(000) -141.5(5) p(Mo Ka), cm-I a, A 2444.8(6) R b, A 4554(3) RW c, A -533(13) B. deg - 1734(12) 3426(12) [Mz(C0)6(&Hdz] (M = Mo, W)," [ M Z ( C O ) ~ ( ~ - C ~(M H ~= )ZI -724(11) Mo, W),20and c l A ~ P P h were 3 ~ ~ prepared as described previ-360( 15) ously. The complexes ClAuPMe3, (ClAu)z(u-dppm),and (ClAu)z- 1120(14) (u-dppe) were synthesized and isolated as solids from ClAu2990(14) 379(15) (thtIz2by adding the appropriate amount of the corresponding -2108(16) mono- or diphosphine. -2386( 16) Preparation of [MZ(~~-P~C~A~PP~~)(CO)~($-C~H~)~I [M -1165(16) = Mo (la), W (lb)]. A solution of Li[Moz(u-~:CzPh)(CO)4(17-136(15) C5H5)214in THF was generated "in situ" by adding dropwise a -702( 15) solution of PhCzLi (1.0 mmol) in THF (15 mL, -78 "C) to a 2616(20) precooled (-78 "C) solution of [ M O Z ( C O ) ~ ( ~ - C(450 ~ H ~mg, )~I 3218(21) 1.0 mmol) in the same solvent. Once the anion was formed, 4588( 18) solid ClAuPPb (490 mg, 1.0 mmol) was added and the mixture 4828(18) 3610(20) was stirred and allowed to warm slowly to room temperature. 2495(13) The resulting red solution was evaporated to dryness and the 2061(12) solid residue was extracted twice (2 x 10 mL) with toluene. 2540(14) Subsequent addition of hexane and cooling overnight (-30 "C) 3968(18) afforded purple microcrystals of compound la: yield 75%. IR 4451(24) (toluene, cm-'1: v(C0) 1959 s, 1898 vs, 1823 s. 31P{1H}NMR 3607(27) (-40 "C, toluene): 6 39.4. lH NMR (25 "C, CsD6): 6 8.0-6.9 2219(21) (m, 20H, Ph), 5.18 (s, 10H, Cp). 13C NMR (25 "C, CeDs): 6 1714(17) 236.2, 234.1 (CO), 134.6-125.6 (Ph), 94.4 (Cp). FAB mass 2959(13) 1689(15) spectrum: mlz 995 [MI+, 967 [M - COl+, 940 [M - 2COl+, 420(16) 883 [M - 4COl+. Anal. Calcd for C~OH~&UMOZO& C, 48.31; 423( 16) H, 3.04. Found: C, 47.98; H, 2.97. 1662(19) A similar procedure was used to prepare the tungsten 2907(17) derivative lb: yield 80%. IR(toluene, cm-'1: v(C0) 1957 s, 5801(13) 1894 vs, 1811 s. 31P{1H} NMR (-40 "C, toluene): 6 39.1. lH 565 1( 16) NMR (25 "C, C6D6): 6 8.0-6.9 (m, 20H, Ph), 5.17 ( 8 , 10H, cp). 6536(18) l3C NMR (25 "c, C&): 6 222.7,222.0 (co), 134.6-125.2 (Ph), 7595(19) 7797(19) 90.3 (Cp). FAB mass spectrum: mlz 1171 [MI+, 1115 [M 69 10(16) 2CO]+, 1087 [M - 3CO]+, 1060 [M - 4CO]+. Anal. Calcd for 5738(12) C~OH~&UO~PWZ: C, 41.05; H, 2.58. Found: C, 41.23; H, 2.69. 5944(14) Preparation of [Mz(lr-PhCzAuPMes)(CO)r($-CaHa)zl[M 6909(15) = Mo (2a), W (2b)l. A solution of Li[Mo~(u-a:C~Ph)(C0)4(q7654(15) C5H&] in THF was generated "in situ" by adding dropwise a 7459(17) solution of PhCzLi (1.0 mmol) in THF (15 mL, -78 "C) to a 6501(15)

precooled (-78 "C) solution of [ M O Z ( C O ) ~ ( ~ - C ~ (450 H ~ )mg, Z] 1.0 mmol) in the same solvent. Once the anion was formed, solid ClAuPMe3 (305 mg, 1.0 mmol) was added and the mixture was stirred and allowed to warm slowly to room temperature. The resulting red solution was evaporated to dryness and the solid residue was extracted twice (2 x 10 mL) with toluene. Subsequent addition of hexane and cooling overnight (-30 "C) afforded purple-red microcrystals of compound 2a: yield 70%. IR (toluene, cm-I): v(C0) 1958 s, 1898 vs, 1823 s. 31P{1H} NMR (-40 "c, toluene): 6 2.2. 'H NMR (25 "c, C6D6): 6 7.97.0 (m, 5H, Ph), 5.24 (s, 10H, Cp), 0.50 (d, 9H, P(CH3)3, WPH) = 9.72 Hz). l3cNMR (25 "c, C&): 6 237.2, 234.5 (co), 130.8-125.4 (Ph), 92.25 (Cp), 14.4 (d, P(CH3)3,J(C-P) = 33.5 Hz). FAB mass spectrum: d z 808 [MI+, 752 [M - 2COl+, 349 Au(PMe3)2+, 273 AuPMe3+. Anal. Calcd for C25H24AuMozOlP: C, 37.15; H, 2.99. Found: C, 37.42; H, 2.97. A similar procedure was used t o prepare the tungsten derivative 2b: yield 75%. IR (toluene, cm-l): v(C0) 1954 s, 1894 vs, 1811 s. 31P{1H}NMR (-40 "C, toluene): 6 2.6. 'H (19)Birdwhistell, R.;Hackett, P.; Manning, A. R. J. Orgunomet. Chem. 1978,157,239. (20)Curtis, M. D.:Fotinos, N. A.: Messerle, L.: Sattelberger, - A. P. Inorg. Chem. 1983,22,1559. (21)Kowala, C.;Swan, J. M. Aust. J. Chem. 1966,19, 547. (22)Us6n, R.;Laguna, A. Orgunomet. Synth. 1986,3 , 324.

ylb

ZJC

Ua

1921.7(3) 203 1.9(3) 1645.2(3) 1676(2) 3699(6) 2946(6) 175(5) 891(5) 3076(7) 2624(8) 731(7) 1189(7) 1039(8) 1609(9) 1539(8) 926(8) 625(7) 1881(12) 2561(10) 2323( 11) 1493(11) 1218(9) 2063(7) 2688(7) 3540(7) 3796(8) 4599(11) 5155(10) 4925(9) 4118(8) 1493(7) 2021(8) 1888(10) 1225(10) 720(9) 838(8) 772(7) 210(7) -483(8) -641(8) -86(9) 622(8) 2502(6) 2598(8) 3203(8) 3715(9) 3644(8) 302 l(7)

1697.8(2) 894.1(2) 153.0(2) 2513(1) 1457(4) -47(4) 863(3) -249(4) 1242(5) 306(5) 588(4) -56(4) 890(5) 1305(6) 1686(5) 1515(5) 1021(5) -758(5) -511(6) -234(5) -288(5) -618(5) 989(4) 648(4) 599(4) 839(5) 762(6) 5 lO(7) 277(7) 316(6) 2978(4) 298 l(5) 3309(6) 3648(6) 3654(5) 3309(5) 2523(4) 2124(5) 2129(6) 2522(7) 2922(7) 2909(5) 2801(4) 3343(4) 3534(5) 3195(6) 2652(6) 2469(5)

390(1) 369(2) 357(1) 387(9) 906(46) 926(47) 726(38) 671(36) 565(46) 557(47) 439(40) 443(41) 609(51) 668(54) 599(50) 577(48) 535(47) 836(72) 812(69) 740(62) 735(64) 683(57) 417(37) 395(36) 467(41) 773(59) 1093(87) 1023(92) 889(76) 768(61) 403(37) 583(48) 758(62) 683(57) 774(62) 656(53) 420(38) 520(46) 701(59) 812(68) 993(74) 707(54) 379(36) 49 l(42) 645(51) 652(54) 658(54) 5 18(44)

"Equivalent isotropic U defined as one-third of the trace of the orthogonalized Uij tensor.

NMR (25 "c, C&): 6 7.9-7.0 (m, 5H, Ph), 5.23 (S, 10H, cp), 0.52 (d, 9H, P(CH3)3, 'J(P-H) = 9.52 Hz). 13C NMR (25 "C, C&): 6 222.9, 222.2 ( c o ) , 131.6-124.9 (Ph), 90.1 (cp), 14.45 (d, P(CH3)3, J(C-P) = 33.0 Hz). FAB mass spectrum: mlz 984 [MI+,928 [M - 2COl+,900 [M - 3COl+, 872 [M - 4COl+, 349 Au(PMe&+, 273 AuPMe3+. Anal. Calcd for CZ~HZ~AUO~PWZ: C, 30.51; H, 2.46. Found: C, 30.83; H, 2.59. Preparation of [OI-dppm){Mz(lr-AuCaPh)(CO)r($-C~H&}al [M = Mo @a),W (3b)l. To a cooled THF (30 mL) solution of Li[Mo2(u-a:CzPh)(CO)4(17-CsHs)zl (0.8 mmol), prepared as described above, was added (ClAu)z(u-dppm)(340 mg, 0.4 mmol) and TlBF4 (233 mg, 0.8 mmol). The mixture was allowed to warm up to -20 "C, and TlCl and LiBF4 salts were removed by filtration. The resulting solution was evaporated t o dryness and the solid residue extracted twice (2 x 15 mL) with precooled toluene. Subsequent addition of hexane and cooling overnight (-30 "C) afforded red microcrystals of the compound 3a: yield 30%. IR (toluene, cm-l): v(C0) 1957 s, 1901 vs, 1825 s. 31P{1H} NMR (-40 "C, toluene): 6 25.1. IH NMR (25 "c, C6D6) 6 7.8-6.9 (m, 30H, Ph), 5.08 (S, 20H, cp), 3.12 (t, PCHzP, 'J(P-H) = 8.9 Hz.

62 Organometallics, Vol. 14, No. 1, 1995

Ferrer et al.

A correction for absorption was applied (maximum and A similar procedure was used to prepare the tungsten minimum values for the transmission factors were 1.217 and derivative 3b: yield 40%. IR (toluene, cm-'): v(C0) 1954 s, 0.809).24 1897 vs, 1815 s. 31P{1H} NMR (-40 "C, toluene): 6 25.1. 'H NMR (25 "c, C&): 6 7.8-6.9 (m, 30H, Ph), 5.06 (s, 20H, cp), The structure was solved by direct and Fourier methods and 3.13 (t,PCHzP, 'J(P-H) = 8.9 Hz. 13CNMR (25 "C, CsDs): 6 refined first by full-matrix least-squares with isotropic thermal 133.9-125.1 (Ph), 90.2 (Cp), 30.0 (PCHzP). parameters and then by full-matrix least-squares with anisoPreparation of [Hg{M~(lr-CCPh)(CO)r(~t-CaHa)2)21 [M = tropic thermal parameters for all non-hydrogen atoms. All Mo (4a), W (4b)l. A solution of Li[Moz@-o:CzPh)(CO)4(9hydrogen atoms were placed at their geometrically calculated C5H5)2] in THF was generated "in situ" by adding dropwise a positions (C-H = 0.96 A) and refined "riding" on the corsolution of PhCzLi (1.0 mmol) in THF (15 mL, -78 "C) to a responding carbon atoms. The final cycles of refinement were precooled (-78 "C) solution of [MOZ(CO)~(~-C~HS)ZI (675 mg, carried out on the basis of 437 variables; after the last cycles, 1.5 mmol) in the same solvent. Once the anion was formed, no parameters shifted by more than 0.61 esd. The biggest solid HgClz (200 mg, 0.75 mmol) was added and the mixture remaining peak (close to a W atom) in the final difference map was stirred and allowed to warm slowly to room temperature. was equivalent to about 1.16 e/A3. In the final cycles of The resulting deep red solution was evaporated to dryness and refinement a weighting scheme, w = K[u2(Fo) gFO2]-' was the solid residue was extracted twice (2 x 10 mL) with toluene. used; at convergence, the K and g values were 0.626 and Subsequent addition of hexane and cooling overnight (-30 "C) 0.0018, respectively. The analytical scattering factors, corafforded purple-red microcrystals of compound 4a: yield 80%; rected for the real and imaginary parts of anomalous disperIR (toluene, cm-l): v(C0) 1976 s, 1916 vs, 1837 s. 'H NMR sions, were taken from ref 25. All calculations were carried (25 "c, C6d6): 6 7.7-6.9 (m, 10H, Ph), 4.98 (9, 20H, cp). l3C out on the GOULD POWERNODE 6040 and ENCORE 91 NMR (25 "c, C&): 6 231.7, 230.2 ( c o ) , 130.0-125.9 (Ph), computers of the "Centro di Studio per la Strutturistica 91.8 (Cp). FAJ3 mass spectrum: m/z 1271 [MI+. Anal. Calcd Difiattometrica" del C.N.R., Parma, Italy, using the SHELXfor CuH30HgMo408: C, 41.58; H, 2.38. Found: C, 41.43; H, 76 and SHELXS-86 systems of crystallographic computer 2.37. programs.26 The final atomic coordinates for the non-hydrogen A similar procedure was used to prepare the tungsten atoms are given in Table 3. The atomic coordinates of the derivative 4b: yield 85%. IR (toluene, cm-'1: v(C0) 1971 s, hydrogen atoms are given in Table SI and the thermal 1907 VS, 1825 S. 'H NMR (25 "c, C&): 6 7.7-6.9 (m, 10H, parameters in Table SI1 of the supplementary material. Ph), 4.97 (s,20H, Cp). '13C NMR (25 "c, C&): 6 220.7,217.1 (CO), 130.8-125.6 (Ph), 90.0 (Cp). FAB mass spectrum: mlz Acknowledgment. Financial support for this work 1623 [MI+. Anal. Calcd for CuH3oHgOsW4: C, 32.57; H, 1.86. was given by the DGICYT (Spain),through Grant PB90Found: C, 32.56; H, 1.90. 0055-C02-01, and by MURST (Italy). We thank X. X-ray Data Collection,Structure Determination, and Huguet and J. Caixac for use of their facilities in Refinement for [W2(lr-PhC2AuPPh~)(CO)r(tl-C5Ha)21 (lb). recording the FAB spectra. A single crystal of ca. 0.20 x 0.24 x 0.32 mm was selected and used for data collection. The crystallographic data are summarized in Table 2. Data were collected at room temSupplementary Material Available: Tables of hydrogen perature on a Philips PW 1100 diffractometer, using the atom coordinates (Table SI), anisotropic thermal parameters graphite-monochromated Mo Ka radiation (3 = 0.71073 A) and for the non-hydrogen atoms (Table SII), and complete bond the 8/28 scan type. The reflections were collected with a distances and angles (Table SIII) for l b (4 pages). Ordering variable scan speed of 3-12' min-l and a scan width from (0 information is given on any current masthead page. - 0.60)" to (0 0.60 0.346 tan 0)'. Of 7638 unique OM9404142 reflections, with 0 in the range 3-27', 3865 with Z B 2dI) were used for the analysis. One standard reflection was monitored every 50 measurements; no significant decay was noticed over (24) Walker, N.; Stuart,D. Acta Crystallogr., Sect. A 1983,39,158. the time of data collection. The individual profiles have been Uzozzoli. F. ComDut. Chem. 1987.11.109. analyzed following the method of Lehmann and L a r ~ e n . ~ ~ -(25) International Tables for' X-Ray Crystallography; Kynoch Press: Birmingham, England, 1974; Vol. IV. Intensities were corrected for Lorentz and polarization effects. (26) Sheldrick, G. M. SHELX-76 Program for crystal structure

+

+

+

(23) Lehmann, M. S.; Larsen, F. K. Acta Cystallogr.,Sect. A 1974, 30,580.

determination. University of Cambridge, England, 1976. SHELXS86 Program for the solution of crystal str&ures. University of Gbttingen, 1986.