3144
Organometallics 1992,11, 3144-3148
An Organoindium Compound Containing an I ndium-Seienium Bond: Synthesis, Propertles, and Molecular Structure of [(Me,CCH,),InSePh], 0. T. Beachley, Jr.,*iia Jesse C. Lee, Jr.,” Henry J. Gysling,Ib Sun-Hua L. Chao,la Melvyn Rowen Churchlll,la and Charles H. Lakela LJ8partmentof Chmdfry, State Unlverslty of New York at Buffab, BMab, New York 14214, and Covporete Research Laboratorkvs, Eastman K d k Company, Rochester, New York 14650 Received M r c h 3, 1992
Summary: An organolndium compound with an In-Se bond, [(Me,CCH,),InSePh] , has been synthesized and characterized by elemental analyses, IR, IH NMR, and 13C NMR spectroscopy, cryoscopic molecular weight studies, and an X-ray structural study. The dimeric molecule crystallizes in the centrosymmetric monoclinic spacegroup P2,lc (No. 14) with a = 18.973 (4) A, b = 10.105 (1) A, c = 19.998 (6) A, 0 = 103.66 (2)O, V = 3725.4 (14) A3, and Z = 4. Diffraction data (Mo K a , 28 = 5-45’) were collected on a Siemens R3mlV automated four-clrcle dlffractometer, and the structure was solved and refined to R = 3.44% and R, = 3.73% for those 2557 umue data wlth lFol > 6a(lFol)(R = 8.35% for all 4891 data). The four-membered In,%, ring has a buttdyenrrngement wlth the phenyl groups In the anti posltlon relathre to the ring. The In-C(neopentyi) distances range from 2.135 (11) to 2.168 (10) A, while InSe bond dlstances range from 2.748 (1) to 2.756 (1) A. There Is some rotational disorder of the methyl groups whln (at least) one of the neopentyl (-CH,CMe,) groups.
Compounds of gallium and indium with bonds to the heavier group 16 elementa selenium and tellurium have been the subject of limited research. The list of organoindium selenides includes only three compounds, [EtJnSe(SiElQ]2,2 [(i-Pr)&~SeEt]~ and [EtInSe],.2 The fmt two compounds in the above aeries were prepared by facile elimination reactions between the triorganoindium compound and the appropriate organo selenol, whereas the third compound was prepared from the firat by a thermal decomposition reaction. None of the above compounds was characterized by an X-ray structural study. An organometallic indium-selenium compound, (Me&CHJJnSePh, which is not a simple adduct, has been prepared by a stoichiometric ligand redistribution reaction between In(SePh), and In(CH2CMe&in pentane at room temperature:
+~ ~ I ( C H ~ C M ~ ~ ) ~ C&12
3(Me3CCH.J2InSePh This reaction avoids the use of benzeneselenol, an unpleasant-smelling compound. The reagent In(SePh):,was readily prepared from indium metal and diphenyl diselenide in refluxing toluene.‘ The new compound (Me3CCHJWePh has been M y characterized by partial (1) (a) State Univeraity of New York at Buffalo. (b) Corporate Research Laboratoriee, Eastman Kodak Co. (2) Vyazankin,N. S.; Bochkarev,M. N.; Charov, A. I. J. Organomet. Chem. 1971,27, 175. (3) Hoffman, G. G.; Faiet, R. J. Orgonomet. Chem. 1990, 391, 1. (4) Annan, T. A; Kumar, R.;Mabrouk, H. E.; Tuck, D. G. Polyhedron 1989, 8, 865.
In(l)-Se(3) In(l ) C (10) In(2)-Se(3) In(2)-C(20) Se(3)
