7633
dramatic variation of -106 exists in the rate constants NzO. The proposed mechanism is quite complicated for the acid and base components of the rate law. and involves copper(I1) in combination with NO In acid solution, substitution of the coordinated ammine functioning as the nitrosylating agent of the amine. is important; however, in basic solution, the reaction By comparison with our study, one might expect that may proceed via a concerted or stepwise attack of NO the lability of Cu(I1) and the fact that no dinitrogen and OH- upon Ru(NH&~+. The dinitrogen complex complex of either oxidation state of copper has been is not produced when either R u ( N H ~ ) ~or~R+U ( N H ~ ) , ~ + reported is suggestive that the N-nitroso amine simply is treated with NO2- in alkaline solution. In general, breaks away from the copper center and then undergoes this suggests that any metal ammine complex which is further decomposition. used in this synthetically useful preparation for diThe reaction of R u ( N H & ~ +with S203?-,OH-, and nitrogen complexes ought to be one which undergoes O2 to produce (NH3)5R~NH2S032+ has been demonreaction with NO,, and has easily dissociatle ammine ~ t r a t e dto~proceed ~ only in basic solution. Considering protons (along with other criteria for metal-nitrogen the substitution inertness of Ru(NH&~’ and the high complex stabili~ation).53.“~ yields obtained for the sulfamate product, it would appear that attack also proceeds on Ru-NH2--. However, Acknowledgment. Partial support to the National one cannot rule out initial attack by S2032-upon the Science Foundation, the donors of the Petroleum Reoctahedron, which facilitates removal of the ammine search Fund, administered by the American Chemical proton. Society, and the Graduate School is gratefully acknowlIn conclusion, we have determined the kinetics and edged. We wish to express our gratitude to Professors mechanism of the reaction between NO and R U ( N H ~ ) ~ ~ M. + Z. Hoffman, N. N. Lichtin, and R . M. Milburn for from pH 3 to -11. Beyond pH 8.3, the reaction is helpful discussions. first order in Ru(III), NO, and OH-, with attack by (53) Yu. G. Borod’ko and A. E. Shilov, Russ. Chem. Rea., 38, 355 NO upon the deprotonated ammine complex. A (1 969). (52) J. N. Armor and H. Taube, Inorg. Chem., 10,1570(1971).
(54) J. E. Fergusson and J. L. Love, Rea. Pure Appl. Chem., 20, 33 (1970).
Derivative Chemistry of Metallocarboranes. Nido 1 1-Atom Metallocarboranes and Their Lewis Base Adducts Chistopher J. Jones, James N. Francis, and M. Frederick Hawthorne* Contribution No. 3135 f r o m the Department of Chemistry, University of California, Los Angeles, California 90024. Received M a y 10, 1973
Abstract: The reaction between X[1-(q-CjH5)-2,4,1-C2CoBsHlo] or X[1,2-C2B~Hl1-3,1’-Co-2’,4’-C~BaH~oland l-CjH5N-7,8,9-C2CoBsHlo] and X[1,2-C2BgH11-3,9’-Co-l 1 ’-CsH:Npyridine affords the nido adducts J1[9-(v1-CjHj)-1 respectively. Oxidation of these species with FeC13 affords the substituted closo compounds 7’,8’-CzB8Hlo]-, X[1-(q-C5H5)-7-C5HjN-2,4,1-C2CoB8Hg]+ and X[1,2-CzBgHll-3,1’-Co-7’-C5H5N-2’,4’-C2BaH9]. Analogous compounds were prepared from X[1-(~-C5H5)-2,4,1-C2CoBaHlo] with piperidine in place of pyridine. The unsubstituted nido metallocarboranes ~9-(~-C5Hs)-7,8,9-C2CoB8Hll]and x[1 ,2-C2BgHll-3,9’-Co-7’,8’-C2B~H11]2were prepared by degradation of the icosahedral compounds [3-(~-CsHsp1,2,3-C2CoBgHll] and [1,2-C2BgHl1-3,3’-C0-1’,2’C2BgHll]-. These compounds could be reversibly protonated to give X[9-(v-C5H5)-7,8,9-C2CoBsH12] and X[1,2C2B9H11-3,9’-Co-7’,8’-C2C~BsH12]which eliminate hydrogen on heating to give [l-(q-C5H5)-2,3,1-C2CoB8H~~] and [1,2-CzBgHll-3,1 ’-Co-2’,3’-C2BsHlD]-. The chemical changes resulting from the replacement of a polyhedral { BH)2+ moiety by {(q-CsH5)Co) 2+ or { 1,2,3-CZCoBgHll} 2+ are discussed.
lthough a large number of metallocarboranes have been prepared1-” since the first report of [1,2-
A
(1) M. F.Hawthorne and G. B. Dunks, Science, 178,462(1972). (2) R. N. Grimes, “Carboranes,” Academic Press, New York, N. Y., 1970. (3) M. F. Hawthorne, D. C. Young, T. D. Andrews, D. V. Howe, R. L. Pilling, A. D. Pitts, M. Reintjes, L. F. Warren, and P. Wegner, J . Amer. Chem. Soc., 90,879 (1968). (4) T. A. George and M. F. Hawthorne, J . Amer. Chem. Soc., 91, 5475 (1969). (5) G. B. Dunks, Ph.D. Dissertation, University of California, Riverside, Calif., 1970. (6) W. J. Evans and M. F. Hawthorne, J . Amer. Chem. Soc., 93, 3063 (1971). (7) G. B. Dunks, M. M. McKown, and M. F. Hawthorne, J . Amer. Chem. Sor., 93,2541 (1971). (8) L. J. Todd, A. R. Burke, A. P. Garber, H. T. Silverstein, and B. N. Storhoff, Inorg. Chem., 9,2175(1970). (9) J. L.Little, P. S. Welcker, N. J. Loy, and L. J. Todd, Inorg. Chem., 9,63 (1970). (10) L. J. Todd, e? al.,J . Organometal. Chem., 50,93(1973).
CzB9Hll-3,3’-Fe-1 ’,2’-CzBgHll]- in 1965,1s119compara(11) J. L. Spencer, M. Green, and F. G. A. Stone, J . Chem. Soc., Chem. Commun., 1178 (1972). (12) L. G. Sneddon and R. N. Grimes, J . Amer. Chem. Soc., 94,
7161 (1972). (13) R. N.Grimes,J. Amer. Chem. Soc., 93,261 (1971). (14) V. R. Miller and R. N. Grimes, J . Amer. Chem. Soc., 95, 2830 (1973). (15) R.N. Grimes, W. J. Rademaker, M. L. Denniston, R. F. Bryan, and P. T Greene, J . Amer. Chem. Soc.. 94,1865 (1972). (16) D. C. Beer, V. R. Miller, L. G. Sneddon, R. N. Grimes. M. Mathew, and G. J. Palenik, J . Amer. Chem. Soc.. 95,3046(1973). (17) J. W. Howard and R. N. Grimes, Inorg. Chem., 11,263 (1972). (18) M. F. Hawthorne, D. C. Young, and P. A. Wegner, J . Amer. Chem. Soc., 87,1818 (1965). (19) The first commo metallocarborane was originally treated as a ?r-bonded metal complex of the (3)-1,2-BsC:H112-ligand (ref 18). However, using the newest IUPAC nomenclature rulcs this compound should be named 2 s a commo polyhedral structure, i.e., [1,2,3-GFeBsH11(3-commo-3’)1 ’,2’,3‘-C2FeB9Hll]-. Since a reader not versed in the detail4 of replacement nomenclature might be led to the
Jones, Francis, Hawthorne 1 Nido 11-Atom Metallocarboranes
7634 Table I. 100-MHz lH Nmr Spectral Data (shifts in ppm tively little is known about the chemistry of metallocarrelative to (CH&Si) borane polyhedra themselves. A variety of substitution reactions involving terminal B-H groups has been Compound and solvent Resonance Assignment o b s e r ~ e d ~ ~ ~as~ -well * as therma.1 rearrangements I. X[9-(v-CjHj)-ll-CjHaN-5.02 Cyclopentadienide involving carbon atom m i g r a t i ~ n . ~However, ~ ~ ~ ~ ~ ~ , ~7,8,9-C2CoB8H1c] ~ in CD3CN -2.591 Carborane CH reactions involving structural changes within the poly-3.491 +11,1 H bridge hedral framework are limited to replacement of { BH} 2+ - 7 . 0 to - 9 . 0 Pyridine by {(q-CjH5)Co}*+ or 1 ~ , ~ , ~ - C Z C O Bto~give H ~poly~]+ IJ, [(CHd4N[XII ,2-CzB9Hil-3.09 Tetramethylm p t a l l i ~ s , insertion * ~ ~ ~ ~ of { (q-C5H5)Co}2 + or “polyhedral ammonium 3,9’-C0-11 ’-CjHjN-7’,8’-2.64) ne:?n,”28 and removal of { BH}?+ or “polyhedral C2B8Hlo]in CDaCN -2.831 Carborane C H ‘i Consequently, we have investigated -3.20/ -3.65) hemistry of metallocarboranes further and have +9.2 H bridge isL .ted a variety of compounds containing 11-atom - 7 . 0 to - 9 . 0 Pyridine polyhedra comprised of one c;obalt, two carbon, and 111, X[9-(&jHj)-ll-C,jHia-4.83 Cyclopentadienide eight boron atoms. The chemical reactions observed NH-7,8,9-C2CoBsHlo]in -3.26‘ -3,56/ Carborane C H (CDdzCO parallel those of the structurally similar carboranes +11 . O H bridge although significant differences in reactivity were found. - 0 . 5 to - 2 . 5 Piperidine C H Adducts Containing Nido Metallocarborane PolyIV, X[ 1-(n-CjHj)-7-CsHaN- 5.67 Cyclopentadienide . . hedra. Both X[1-(q-CgHj)-2,4,1-C2CoB8Hlo] and X-4.16) 2,4,1-CzC0BsHgI[PFsl 6 , / Carborane CH in CDICN [1 99H11-3,1 ’-Co-2‘,4’-C&H10]- reacted with pyri- 7 . 0 to - 9 . 0 Pyridine i Tive the red adducts I and I1 in 85 and 70% -5.55 0 . 5 CHzC12 of pectively. The 100-MHz ‘H nmr spectrum solvation of I exhibited resonances owing to the CjHjV, X[1,2-C2BsHll-3,1’-CO-5.76) ridine, and two nonequivalent carborane CH 7’-CjH;N-2‘,4’-C:BsHg] in -4.211 Carborane C H (CDILCO -2.96( in addition, a broad resonance was observed -2.54) Jpm which we assign to a bridge proton. The - 7 . 0 to - 9 . 0 Pyridine ’H nmr spectrum of I1 similarly showed a - 5.42 0 . 5 C H G of at $9.2 ppm assigned to a bridge proton, solvation VI, X[1-(11-CjHj)-7-C,H1oN-4.52 Cyclopentadienide other resonances attributable to pyridine, ‘iivalent carborane CH groups, and the 2,4,l-CzCoBsHg] in C6De -4’84) Carborane C H - 2 96 nmonium cation (Table I). The mass - 0 . 5 to - 2 . 5 Piperidyl exhibited a cutoff at mie 325 consistent VII, [(CH3)4N12X[lr2-C2B9Hll- - 3. 42a Tetramethylnula C12H20B8NCo. However, the ion 3,9‘-Co-7’,8’-C2BsH1,]in - 2. 16b) ammonium CD3CN - 22, 8.46b 5b/ Carborane C H the parent peak array was unlike that suggested that hydrogen was being lost -3.34bJ ular ion, as has been noted previously H bridge f3.956 :tallo~arborane.~~ The 80.5-MHz I l B Tetramethyl-3.06 VIIJ, [(CHa)aN]X[1,2-CzBgHiiammonium -2.22 3,9’-Co-7‘,8’-C2BsH12]in of I (Figure la) consisted of seven -2.941 CDaCN 1 and a singlet of area 1 at -4.3 ppm. Carborane C H -3.40/ lvas consistent with the presence of a -4.02) e substituent on boron and the absence + l . 53b nmetry. The 80.5-MHz “B nmr spec+6. lob) H bridge Tetramethyl-3.06 ire 2a) was complicated by the extensive ammonium mances. The spectrum was simplified -4.18 Carborane CH ‘H decoupling of the terminal {BH} -6.621 :odd be qualitatively fitted to the overCyclopentadienide -4.69 Tetramethyl-3.10 7,8,9-CzCoB8Hll]in a of I and [3-(q-CjHj)-1,2,3-C?CoBgHll]. - I
ammonium
CDICN compound contains t w o iron atoms, we have simplified m e contained in this paper in such a way as to observe IL .>bering while eliminating the -comma- description. Thus, the c&...,,ound in questions appears here as [1,2-C2B~Hll-3,3’-Fe-l l.2‘CnBgH111- with the point of polyhedral fusion designated by -3,3’-Fe-. (20) M. F. Hawthorne, L. F. Warren, K . P. Callahan, and N. F. Travers, J . Amer. Chem. SOC.,93,2407(1971). (21) J. N. Francis and M. F. Hawthorne, Inorg. Chem., 10, 594 (1971). (22) J. N. Francis, C. J. Jones, and M. F. Hawthorne, J . Amer. Chem. Soc., 94,4878 (1972). (23) B. M. Graybill and M . F. Hawthorne, Inorg. Chem., 8 , 1799 (1969). (24) L. F. Warren and M. F. Hawthorne, J . Amer. Chem. SOC.,92, 1157 (1970). (25) M. I
