Inorganic Chemistry, Vol. 9, No. 7 , 1970 1769
NOTES be considerably lower, perhaps less than L a ( f ~ d ) ~Al. though volatilization does not appear to be a practical method for separating U(fod)d, Np(fod),, and Pu(fod)4, i t may be useful for separating these actinides from light lanthanides and trivalent actinides.
Acknowledgments.-The authors are grateful to K . Ernst, Lawrence Radiation Laboratory, Livermore, Calif., for mass spectrometric information and to W. J. Kerrigan for assistance in construction of the apparatus.
Notes this study were prepared as previously reported,j with the excepCONTRIBUTION XO.2605 FROM THE INSTITUTE FOR ATOMICRESEARCH A N D DEPARTMENT OF CHEMISTRY, tion of the compounds noted below. IOWA STATEUNIVERSITY,AMES, IOWA 50010 [ (CIHO),N] 3 [ (Nb&h)I,] .-A compound approaching this composition was prepared by dissolving,Nb6Cllr.8H20 in ethanol, refluxing with a large excess of tetra-n-butylammonium iodide, Chemistry of Polynuclear Metal Halides. VIII. cooling, and filtering. The solution was then evaporated to near dryness, and the above procedure was repeated in a fresh and Infrared Spectra of Some Nb6X12"+ solution of ethanol-((C4H!,)4N)I. Upon concentrating and cooling TaeXlzn+ Derivatives' the solution, dark crystals were obtained. These were filtered, washed successively with chloroform and ether, and then dried in Y U C U O . A n a l . Calcd for C&l~~sNsNbeCl&: Nb, 22.56; BY P. B. FLEMING, J. L. MEYER,W. K. GRINDSTAFF, C1, 17.22; I , 30.81; C, 23.31; H, 4.41. Found: S b , 24.21; A N D R. E. MCCARLEY C1, 17.65; I, 28.84; C, 21.63; H, 4.03; CI/Nb, 1.91; I/Nb, 0.87. Received August 22, 1969 [ (CH3)rN],l(Nb&llz)C&].-This compound was prepared acRecent studies of the infrared spectra of compounds cording to a method developed by Koknat.6 Complete details of the synthesis will be given in a subsequent paper. A n a l . containing M&Zn+ cluster species have been reported by Boorman and Straughaq2 Mackay and S ~ h n e i d e r , ~ Calcd for CleH~&Nb&lls: Nb, 37.36; C1, 42.77; N, 3.75; C, 12.88; H, 3.24. Found: Nb, 37 28; C1, 42.54; IY,3.82; C, and M a t t e s 4 Certain characteristic bands arising 12.78; H, 3.28; CI/Nb, 2.99. from the M6X122f(M = Nb or T a ; X = C1 or Br) Several compounds containing DMSO (dimethyl sulfoxide) are cluster units were first identified by Boorman and reported in the results. These were prepared as follows, but their composition is nominally that reported since analytical Straughan2 in derivatives where the associated anions data were not obtained. The hexakis adducts [(MsXn)(DMand coordinated neutral donor ligands were varied, e.g., so)6](clo4)n (M = Nb, T a ; X = C1, Br) were synthesized by among C1-, Br-, SO4*-, BF4-, HzO, and C5H,N. dissolving the appropriate cluster hydrate ( M G X I L ) X ~ . ? ? H inZaO Mackay and Schpeider3 reported a more extensive inminimum volume of DMSO, adding a small excess of- AgC104 to vestigation of Nb&112"+ complexes in each of the states precipitate the outer halide ligands, and stirring the solution overnight. The silver halide precipitate was removed by filtrawith n = 2 , 3, or 4. Principally by exchanging outer ligands Y and L in the complexes ( N b ~ c 1 1 ~ ) Y ~ -tion, and the desired perchlorate salt was precipitated by the addition of chloroform, filtered, washed successively with eth+, where m is the cluster oxidation state, they anol L6-n(---n) and ether, and dried in air. These perchlorate compounds identified four allowed ir bands arising from the Nb&z weye found to be shock sensitive and hazardous, but small amounts cluster unit and also those arising from vibrations of the (1-10 mg) could be handled normally with caution. The compounds of nominal compositions (?jb6Cllt)Br~outer Nb-Y or Nb-L bonds. (DMS0)r and ( T ~ & ~ ~ Z ) C ~ ~ ( D were M Sprepared O)~ by dissolving I n the most recent study Mattes4 reported the ir the appropriate hydrated cluster halide in DMSO, adding chlorospectra for a larger number of derivatives (MsX1Z)Xn, form or ether to precipitate the compound, washing with the with M = Nb, T a ; X = F, C1, Br, I ; n = 2, 3, 4. A same solvent, and drying in air. The compound (Nb6Cl12)C13normal-coordinate analysis was performed in the at(DMS0)s was prepared by dissolving a weighed sample of ((C~H~)~N)~[(N~~C~IZ)CI~] in a few milliliters of DMSO, adding tempt unambiguously to assign the observed bands the calculated quantity of AgCIOd to precipitate three of the and calculate force constants. However ir data terminal chloride ligands per mole of cluster, and stirring for 3 hr. which we have obtained indicate that certain of the asAfter filtering to remove AgCl, the desired compound was presignments made in the previous studies are incorrect. cipitated with addition of a large volume of chloroform, filtered, Since the Raman spectra needed to confirm the assignand washed with the same solvent. The product apparently contained extra DMSO of crystallization and may be formulated ments finally will be difficult to obtain on these highly as [(~b6Cllz)C13(DMSO)s] .3DMSO. A n a l . Calcd for Nbscolored compounds, we report here the results of our C ~ ~ S C ~ Z H ~Nb, BS~ 35.8; O ~ : CI, 34.2; C, 9.3; H , 2.3. Found: study, with suggestions for changes in previous ir band h'b,36.1; C1,35.7; C, 10.4; H, 2.6. assignments. Infrared Spectra.-Spectra were measured over the region 600-4000 cm-l on a Beckman IR-7 instrument and over the reExperimental Section ( 5 ) (a) B. G. Hughes, J. L. Meyer, P. B. Fleming, and R. E. McCarley, Preparation of Compounds.-Most of the compounds used in (1) Work performed in the Ames Laboratory of the U. S. Atomic Energy Commission. (2) P. M. Boorman and B. P. Straughan, J. Chem. Soc., 1514 (1966). (3) R. A. Mackay and R. F. Schneider, Inorg. Chem., 7 , 455 (1968). (4) R . Mattes, Z . Anovg. A&. Chem.. 364, 279 (1969).
Inorg. Chem., 9, 1343 (1970); (b) P. B. Fleming, T. A. Dougherty, and R. E. McCarley, J . Amer. Chem. Soc., 89, 159 (1967); (c) P. B. Fleming, L. A. Mueller, and I
