3342
Synthesis of Transition Metal-Monocarbon Carborane Complexes Sir :
We wish t o report the facile synthesis of complexes of the BloHloCH3-and BloHloCNHzR2-ions with several transition meta1s.l The syntheses are based on two general reactions very closely related to the preparative methods recently described for the (3)-1,2-dicarbollyl sandwich complexes : (1) Na3B10H10CHand anhydrous metal chloride, and (2) CsBloH12CH,aqueous sodium hydroxide, and metal chloride. 293
Ni'V[B~oHloNH(CH3)C3H7]2. The llB nmr spectra of these amine derivatives extend over 29 ppm and are similar to those of the unsubstituted complexes but are not as well resolved. Analyses of the compounds are given in Table I. The striking similarity in properties of the metal complexes reported in this paper and their isoelectronic dicarbollide analogs leads us to suggest that the transition metal in these compounds is ir-bonded to the open face of two monocarbon carborane (carbollide) icosahedral fragments. Thus the Co*" species I1 and VI are apparent analogs of the cobalticinium ion
Table I. Analyses Calculated, Compound
C
[(CH?)~N~~CO(B~OH~OCH)Z Cs&"(Bi oHiaCH)z [(CH8)4Nl3Fe(BloHl~CH)z
30.91 4.09 31.05 (CHI)~NCO(B~OH~OCNH*CZH~)~ 24.83 N~(B~OHIOCNH~C~H~~ 22.01
7
H
N
B
Metal
C
H
10.74 3.78 10.80 9.59 8.76
7.72
39.78 36.84 40.07 44.70 49.45
10.84 10.00 10.30 12.18 13.44
30.99 3.77 30.92 25.09 22.05
10.80 3.90 10.98 9.63 9.08
...
7.78 8.69 6.42
Found, N
B
Metal
...
39.73 36.55
7.59 8.67 6.40
... ...
10.6 9.8 9.8 12.6 12.9
7.58
...
and the Fe"' species IV analogous to the ferricinium The BloHloCH3-ion is readily prepared as a sparingly ion. A single crystal X-ray study now in progress soluble sodium salt (I) by deamination and deprotonashould lend support to this postulate. tion of BloH12CN(CH3)3with sodium metal in tetraSalts of the (BloHloCH)Mn(C0)32-and CuII'(B1ohydrofuran (THF).4 Addition of I to a solution of anhydrous CoClz in T H F yielded a precipitate of HloCH)23- ions have also been obtained from BrMncobalt metal and sodium chloride. The Co"'(Blo(CO)5 and copper(I1) acetylacetonate, respectively, by the anhydrous route with Na3BlOHIOCH.The IlB HloCH)z3-ion (11) was isolated as either f i e cesium or nmr spectra of these ions which extend over 20 ppm tetramethylammonium salt. The salts of I1 are diaare similar to one another but dissimilar to the spectra (e): 279 (36,600) and 422 magnetic and yellow [A, of the nickel and cobalt derivatives. mp (38211. Further synthetic and structural studies of these The second type of reaction is illustrated by the new carbollyl-transition metal complexes are in synthesis of the Ni'V(BloHloCH)2z-ion (111). An aqueous mixture of NiClz (13.5 mmoles), CsBloH12CH progress and will be reported at a later date. (22.1 mmoles), and sodium hydroxide (270 mmoles) Acknowledgment. The authors wish to thank Mr. was heated at 40" with air injection for 20 hr. The J. Nemeth for the microanalyses, Dr. Donald F. Gaines, yellow, diamagnetic cesium salt of I11 could be isoUniversity of Wisconsin, for the 32-Mc llB nmr, and lated in yields as high as 82% from this reaction. the National Science Foundation for support under By this method one can also obtain good yields of I1 Grant GP-4982. and salts of the red Fe111(B10HloCH)23ion (IV). David E. Hyatt, John L. Little, John T. Moran Preliminary X-ray data on Cs2Ni'V(BloH10CH)z Frederick R. Scholer, Lee J. Todd yield the cell parameters: a = 20.25, b = 12.77, c = The W . A . Noyes Laboratory, Uiiioersity of Illinois 14.64 A, z = 8, d(ca1cd) 2.08, d(found) 2.04. The llB Urbatta, Illinois 61801 nmr spectra of I1 and I11 extend over 29 ppm and are Receiced April 5, 1967 grossly similar to one another but have not been completely interpreted. The paramagnetic ion (IV) has Transition Metal Complexes of B10HloCNH32a llB nmr spectrum which extends over approximately and BloHloCH3300 ppm and does not appear to show llB--lH ~ o u p l i n g . ~ Treatment of BloH1zCNHzC3H76 with NiClz in aqueSir: ous base gives in good yield, orange, diamagnetic A series of sandwich complexes of transition metals Ni'V(BloHloCNH2C3H7)z(V). The mass spectrum of with the BgCzHllZ-anion has been reported by HawV cuts off sharply at m/e 444 corresponding to the parent thorne and co-workers. ' These complexes are form2Ni+. Orange, diamagnetic ion, 12C8'H 38 l4N2'BZo6 ally analogous to metallocenes because the metal in (CH3)4NCo11'(BloHloCHNHzCzH5)2 (VI) was obtained both cases is bonded to a pentagonal face which can in the same manner. Methylation of V with sodium contribute three bonding molecular orbitals and six bicarbonate and methyl iodide gives dark orange electrons. 2, This communication reports the preparation of simi(1) We are indebted to Dr. Knoth, who recently advised us of his work in this area: W. H. Knoth, J . Am. Chem. Soc., 89, 3342 (1967). lar metal complexes of BloHloCNH32-and BloHlo(2) 1818 (3) (4) (5)
M. F. Hawthorne, D. C. Young, and P. A. Wegner, ibid., 87,
L. F. Warren, Jr., and M. F. Hawthorne, ibid., 89, 470 (1967). W. H. Knoth, ibid., 89, 1274 (1967). A similar broad, decoupled spectrum was observed for the FeIII(BGH11)z- ion; see ref 2. (6) D. E. Hyatt, D. A. Owen, and L. J. Todd, Inorg. Chem., 5 ,
(1) (a) M. F. Hawthorne, D. C. Young, and P. A. Wegner, J . Am. Chem. Soc., 87, 1818 (1965); (b) M. F. Hawthorne and T. D. Andrews, Chem. Comrnun., 443 (1965); (c) L. F. Warren, Jr., and M. F. Hawthorne, J . Am. Chem. Soc., 89,470 (1967). (2) M. F. Hawthorne and R. C. Pilling, ibid., 87,3987 (1965). (3) A. Zalkin, D. H. Templeton, and T. E. Hopkins, ibid., 87, 3988
1749 (1966).
(1965).
(1965).
Journal of the American Chemical Society
1 89:13 I June 21,1967
