Organometallics 1991,10, 3764-3766
3764
Notes Tetramethyl-cyclo -tetraarsaoxane, cyclo-(CH,AsO),: Its Crystal Structure and That of Its Methylcymantrene Complex [Cp'Mn( CO)2]2[cyclo-( CH,AsO),] Anthony4 DiMaio and Arnold L. Rheingold" Department of Chemistry and Biochemistry and the Center for Catawic Science and Technology, Universm of Delaware, Newark, Delaware 19716 Received April 9, 199 1
Summary: The tetrameric arsenic-oxygen heterocycle tetramethyl-cyclo-tetraarsaoxane, cyclo-(CH,AsO),, is obtained as a crystalline single phase from the aerobic oxidation of homocyclic pentamethyl-cyclo-pentaarsine, cyclo-(CH,As),, via a metal-carbonyl template reaction wing Mn&O),o. A chair-boat ring conformation for this cyclooctane analogue has been determined crystallographically: C,H,,As 04,monoclinic, P2,ln, a = 9.229 (3) A, b = 8.848 (3) c = 14.760 (5) A, 6 95.04 (3)O, V = 1200.6 (7) A3, Z = 4, R ( F ) = 5.28%. The arsaoxane ring readily forms complexes in which two of the four arsenic atoms function as twoelectron donors. With methylcymantrene, Cp'Mn(CO),, [Cp'Mn(CO),] [cyclo(CH,AsO),] is formed. The eight-membered ring is found crystallographically in a chair conformation, likely for steric reasons: C,,,HH,As4Mn,0,, monoclinic, P2,1nI a = 10.842 (2) A, b = 9.418 (2) A, c = 14.146 (3) A, 6 = 107.49 (2)O, V = 1377.7 (5) A3, Z = 4, R ( F ) = 3.59%.
1,
,
We recently reported that the heterocyclic, alternating arsenic-oxygen ring systems, methylarsaoxanes,' cyclo(CH3AsO), (n = 3 or 4), were attractive oxygen-transfer agents in organometallic oxidations due to their ability to retain "soft", trivalent arsenic ligand properties throughout the oxidation process.2 Thus, in both reduced and oxidized forms, the potential exists for the performance of stereospecific oxygen-atom transfers. Coordination of the arsenic species and substrate is maintained before, during, and after transfer. In the earlier communication, it was briefly mentioned that the ligand properties of the cyclotetramer, cyclo-(CH3AsO), (l),had been demonstrated by the formation of complexes containing intact arsaoxane rings. We wish now to describe this work in more detail and to specifically report the formation and structure of (2) one such complex, [Cp'Mn(C0)2]2[cyclo-(CH3AsO)4] (Cp' = $-CH3C6H4),and also that of the uncoordinated cyclotetramer (1). There are surprisingly few prior reports of complexes of alternating atom, heterocyclic cyclo-(REO), (E = group 15 element) systems when compared to E-N ring systems. Knowledge of E = P complexes is limited to reports of triand tetrameric ring systems serendipitously assembled from (i-PrzN)zP(0)H,3 and the only E = As complex is a (1) Compounds possessing the empirical formula CH3As0 have been known by many different names: arsenosomethane, oxymethylarsine, methyloxoareine,and methylamine oxide. According to the moat modem nomenclature, either methylarsoxane or methylarsaoxane is correct. Preference is given to the latter due to ita greater clarity when spoken. (2) Harper, J. R.; Rheingold, A. L. J.Am. Chem. SOC.1990,112,4037.
cyclohexameric system, [MO(CO)~]~[C~C~O-(CH~A~O)]~, also serendipitously assembled., Arsaoxanes have been previously prepared by a wide variety of procedures, the most important of which have been the reduction of arsonic acids (usually by sulfur dioxide), the hydrolysis of organoarsenic dihalides, and the oxidation of primary arsines or cyclopolyarsines.6 These procedures often lead to the complex mixtures of cyclic and linear oligomers; equilibrium compositions for methylarsaoxanes have been studied by NMR methods.6 Direct contact of air with pentamethyl-cyclo-pentaarsine, cyclo-(CH,As), (3), is pyrophoric, but in solution, 3 may be slowly oxidized by air to form oligomeric polymethylpolyarsaoxanes. These same oligomers are present at levels of 5-2090 in all samples of 3 prepared from aqueous reagents, e.g., the hypophosphorous acid reduction of methylarsonic acid. The arsaoxanes may be identified by the envelope of 'H NMR resonances 0.1-0.3 ppm =field from 3.' (These upfield peaks have been previously incorrectly identified as other oligomers and conformers of 3, and not their oxidation products.) Pure samples of 3, either prepared from methylarsine and dibenzylmercurp or purified by chromatography, thermolytically (170 "C, 48 h) react with M2(CO)',, (M = Mn or Re) in toluene, first to form [Mn(CO),][p(CH,),As)] (4) and (cyclo-[(CH3As)7As]Mn(CO)4JMn2(CO)6 (5).9J0 If air is admitted to this system during workup (in the first instance inadvertently), a singlet grows rapidly in the 'H NMR spectrum at 6 1.41, indicating the formation of cyclo-(CH,AsO),. On cooling, crystalline cyclotetramer is obtained in good yield. Under similar conditions, in the absence of metallic coreactants, 15-20 resonances are found in this region, indicating the presence of an oligomeric family of species. The polynuclear metal complex is apparently serving as a template for the formation of single-dimension arsaoxane species. Photolysis of a mixture of Cp'Mn(CO), and the homocycle 3 produces a complex identified spectroscopically as containing an intact five-membered pentaarsenic ring with (3) Wong, E. H.; Turnbull, M. M.; Gabe, E. J.; L e , F. L.; LePage, Y.
J. Chem. SOC.,Chem. Commun. 1983, 776. Wong, E. H.; Gabe, E. J.; Charland, J.-P. J.Chem. SOC., Chem. Commun. 1988,1632. Wong,E. H.; Gabe, E. J.; Lee, F. L.; J. Chem. SOC.,Chem. Commun. 1989, 1236.
(4) Rheingold, A. L.; DiMaio, A.-J. Organometallics 1986, 5, 393. (5) Doak, G. 0.;Freedman, L. D. Organometallic Compounds of Arsenic, Antimony and Bismuth; Wiley: New York, 1970. (6) (a) Durand, M.; Laurent, J.-P. J. Organomet. Chem. 1974,77,226. (b) Marsmann, H. C.;Van Wazer, J. R. J.Am. Chem. SOC. 1970,92,3969. (7) Rheingold, A. L. Organomet. Synth. 1986, 3, 618. (8)Choudhury, P.; Rheingold, A. L. J. Organomet. Chem. 1977,128, 155.
(9)Elmes, P. S.;West, B. 0. J. Organomet. Chem. 1971, 32, 366. (IO) DiMaio, A,-J.; Rheingold, A. L. Organometallics 1987, 6, 1138.
0276-7333f 91f 2310-3764$02.50f 0 0 1991 American Chemical Society
Notes
Organometallics, Vol. 10, No. 10, 1991 3765 Table 111. Atomic Coordinates (X104)and Isotropic Thermal Parameters (A* X 10’) for 2
Ngure 1. Molecular structure of cyclo-(CH&O), (1) drawn with 40% probability ellipsoids. Table I. CrYstalloPraDhic Data for 1 and 2 1
formula fw space group cryst system a, A
b, A
c, A
8, deg
V,AS
2 cryst dimens, mm cryst color D(calc), g/cm3 ~ ( M Ko a ) , cm-l temp, OC T(max)/ T(min) diffractometer monochromator scan technique radiation 28 scan range, deg rflns collected indpt rflns R(merg), % indpt rflns obsd (nu(FJ) std rflns var in stds, 90
R(F), ?% R(wF), % A/a(max) Ap, e A-3 NOIN”
GOF
2
(a) Crystal Parameters C4H1&404 ~&16AS&h08 423.78 804.04 m1/n m1/n monoclinic monoclinic 9.229 (3) 10.842 (2) 8.848 (3) 9.418 (2) 14.760 (5) 14.146 (3) 95.04 (3) 107.49 (2) 1200.6 (7) 1377.7 (5) 4 2 0.21 X 0.21 X 0.36 0.30 X 0.30 X 0.38 pale yellow yellow 2.34 1.94 110.01 56.8 23 23 2.30 1.56 (b) Data Collection Nicolet R3m graphite Mo KOL(A = 0.71073 A) 4-55 4-50 2111 2700 1884 2424 5.70 2.90 1704 (n = 5) 1175 (n = 5) 3 stdl197 rflns
3 atd/197 rflns
