J . Am. Chem. So?. 1985, 107, 7226-7227
7226
These results indicate that phthalocyanine “molecular metal” chemistry is considerably broader than that involving only halogen counterions. In the case of highly conductive Ni(Pc)(BF,)o.,3. similarities to halogenated analogues in crystal and band structure are accompanied by significant differences in transport/metalto-semiconductor transition characteristics. Further phthalocyanine counterion effects are under investigation. A c k n o w l e d g m e n t This research was supported by the N S F through the Northwestern Materials Research Center (Grant DMRX2-16972, T.J.M. and C.R.K.) and by the Office of Naval Research (T.J.M.). We thank Prof. S. H. Carr for helpful comments. (19) Gutfreund. H.; Entin-Wohlman, 0.; Weger. Crysr. 1985, 119. 457-466 and references therein.
Figure 1. Structure of
(9-C,H,),,V,,@,,(N(CH,),),.
M. Mol. Cryst. Liy.
Figure 2.
Structure of (q-C5H5),4V,6014.
Organometallic Clusters Containing Oxygen Atoms: The ESR of I showed an assymetrical eight-line spectrum Preparation, Structure, and Properties of typical of vanadium in a low-symmetry environment. The ’ H (n-CsH~)llV130,~(N(CH,)3)~ and ( ~ - C S H S ) I ~ V I ~ O Z ~ N ~ M R showed a broad, weak, symmetrical resonance at -79.4, a multiplet a t -7.15. and a singlet at -2.29 ppm. The latter Dimeric Derivatives of (T&H~)~V~O~ resonances had an intensitv ratio of 2.61. We assinn the resonance at -79.4 ppm to an qS-CsH5group attached to paramagnetic Frank Bottomley,’ Daniel E. Paez. and Peter S. White vanadium. the resonance at -7.15 m m to nS-C,H, attached to diamagnetic vanadium, and that a i I 2 . 2 9 ppm io the N(CH,)?. Department o/ Chemistry. Uniuersity of New Brunswick This interpretation means that the Cp5V60, units are diamagnetic and the vanadium(ll1) in the bridge has two unpaired electrons. Received August 5, 1985 The diamagnetism and regularity of the Cp,V608 may be rationalized by arguments developed for Cp6M6A,.’ The Cp,(rWe described previously Cp5V,06 and Cp,Cr40,’ (Cp = q5O)V,Os units are derivatives of Cp,V,O, in which an O R group C5Hs) which with Cp6Ti60, described by Caulton et al., form replaces one Cp. This leaves the number of cluster electrons at a series of (CpM),(p,-0), clusters. In a theoretical study we eight but increases the cluster orbitals by two. If the unique suggested that in each cluster there were 12 orbitals occupied by vanadium lies on z the four orbitals it contributes to the cluster 2 (Cp,Ti,O,), 8 (Cp,V,06). or 12 (Cp,Cr,O,) electrons, and a are the same two as in Cp6V,0,, dx*+ and d2*,plus d,, and dy2. variety of more or less distorted octahedral (CpM),O,, trigonal Of these, dz*+ is nonbonding and the other three are antibonding bipyramidal (CpM),O,, and tetrahedral (CpM),O, clusters should counterparts of V-0 bonds. In addition d,, is the antibonding be obtainable.’ We report here the preparation of Cp6V608and counterpart of the *-bond between the bridnine - - oxvnen ._ and vatwo remarkable derivatives of it, [(Cp5V,(pl-O),),((p-O)~VCpnadium. Therefore d,*,i remains localized on the unique vana( N ( C H i ) J d I (1) and [ ( ~ P s V ~ ( ~ ~ - ~ ) ~ ) ~ ( ~ P V(11). ) , ( p r ~ ) sdium l and is occupied by two electrons; d,, and d,,7contribute to When Cp,V was oxidized by (CH,),NO in toluene a black solid the cluster and d;, is ofhigh energy. Oniy six eiectrons occupy and a black-brown solution were obtained. The solid was not the 12 cluster orbitals. The configuration is a , t e d ; therefore crystalline but mass spectrometry (all m l e peaks corresponding CpsV60, is diamagnetic and undistorted. O ) , microanalysis (found, C, 42.5; to Cp,V608+ with m = 6 When Cp,V was oxidized by (CH,),NO in tetrahydrofuran a H, 3.9%:. calcd for C,,H1,V6O8, C, 43.7; H, 3.7%) and ‘H N M R black, diamagnetic, crystalline solid of formula Cp,,V,,O,, was (singlet at -171.4 ppm) established it as paramagnetic Cp6V,08. obtained. It t w is derived from Cp6V60,: two Cp,V60, are linked The solution deposited large crystals on storage at 5 OC. These by (CpV),(p,-O), (Figure 2).6 The latter is a rectangle of were shown to be 1 by X-ray crystallography (Figure I)! The vanadium with pairs of oxygen along the edges; the connections cluster is derived from Cp6V,0, by removal of one Cp and linking to CpJV608are diagonally opposed oxygens (V-0 1.701 ( I 3) A). of two Cp,V60, fragments via the oxygen of (CpV(N(CH,),),The V-V distances in the Cp,V60, units average 2.900 ( 5 , 21) ( p - O ) > ) . The CpsV60, units contain regular octahedra of vaand the V-0 distances 1.942 (14, 67) 8,. very similar to 1. In nadium with an average V-V distance of 2.906 (4, 29) The the (CpV),(p,-O)8 bridge the V-V distances are 2.989 (6) and oxygen atoms lie over the triangular faces with an average V - 0 3.296 (6) 8, and the V-0 distance to the doubly bridging oxygens distance of 1.940 (IO. 55) 8,. The V-V distances are similar to 2.020 (14, 29) 8, but to the two triply bridging ones 2.179 (14. the Ti-Ti in Cp,Ti,O,, 2.891 8, ( I , l4).’ The V-0 distance to 26). the linking oxygen is 1.679 (15) A. These clusters are extreme cases of those obtained by binding organometallic fragments to polyoxometalate { [(C,H8)Rh],(~is-Nb,W,0,,),~~~’ is a spectacular example. Both 1 and ( I ) Bottomlcy. F.: Paer. D. E.;White. P.S. J . Am. Chenr. Sor. 1982. 104. II are true molecular clusters, being highly soluble in toluene.
