C29H48HfO2Si2, orthorhombic, Pnma (no. 62), a = 16.8546(4) Å= 14.4139(6) Å= 12.1421(3) Å, V= 2949.8 Å3, Z = 4, Rgt(F) = 0.020, WR ref(F2) = 0.041, T= 200 K. © by Oldenbourg Wissenschaftsverlag

Beweries, T.

Burlakov, V.V.

Rosenthal, U.

Spannenberg, A.

English

Repositorium für Naturwissenschaften und Technik

Crystal structure of 1,1-bis(pentamethylcyclopentadienyl)-4,5-bis(trimethylsilyl)-1-hafnafuran-3-one, Hf(C10H15)2(Me3SiC2SiMe3CO2)Torsten BeweriesI, Vladimir V. BurlakovII, Uwe RosenthalI and Anke Spannenberg*,II Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, GermanyII A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov St. 28, 117813 Moscow, RussiaReceived November 4, 2008, accepted and available on-line January 21, 2009; CCDC no. 1267/2498AbstractC29H48HfO2Si2, orthorhombic, Pnma (no. 62),a = 16.8546(4) Å, b = 14.4139(6) Å, c = 12.1421(3) Å,V = 2949.8 Å3, Z = 4, Rgt(F) = 0.020, wRref(F2) = 0.041,T = 200 K.Source of materialCp*2Hf(+2-Me3SiC2SiMe3) (0.220 g, 0.35 mmol) was dissolvedin 10 ml n-hexane and filtered. The argon atmosphere was re-moved in vacuum and the Schlenk tube was flushed with carbondioxide. The colour changed immediately from blue to yellow, af-ter two hours at room temperature yellow needles formed whichwere seperated by decanting of the mother liquor, washed withcold n-hexane and dried in vacuum to give 0.136 g (0.21 mmol, 59%) of the title compound.DiscussionTitanocene and zirconocene alkyne complexes have been knownfor several years now, recently we have also accomplished thesynthesis of first hafnocene alkyne complexes [1,2]. To investi-gate the reactivity of such complexes, simple reactions, e.g. withwater or carbon dioxide are possible, giving useful informationon the reaction behaviour with respect to ligand dissociation or in-sertion reactions.The molecular structure of the title compound displays a benthafnocene fragment with a hafnafuranone unit. The bond lengthC1—C2 of 1.373(6) Å is in the range of a double bond. Moreoverthe relevant bond angles of the metallacycle (O1−Hf1−C177.0(1)°, Si1−C1−C2 121.1(3)°, Si2−C2−C1 137.6(3)°) are inthe expected range and resemble those of the corresponding zir-conium complex (O1−Zr−C13 75.5(2)°, Si1−C13−C12123.0(4)°, Si2−C12−C13 137.2(4)°) [3]. Whereas the reaction ofthe similar cyclopentadienyl substituted hafnocene alkyne com-plex Cp2Hf(PMe3)(+2-Me3SiC2SiMe3) with carbon dioxide re-sults in the formation of a dinuclear complex [4], the higher stericdemand of the pentamethylcyclopentadienyl ligand prevents thedimerization of the product. The described reaction pattern showsthe trend of coupling and insertion reactions instead of alkyne dis-sociation reactions for hafnocene alkyne complexes compared tosimilar titanium and zirconium species. This is in agreement withthe observations made before [2].Z. Kristallogr. NCS 224 (2009) 93-94 / DOI 10.1524/ncrs.2009.0046 93© by Oldenbourg Wissenschaftsverlag, MünchenCrystal: yellow prism, size 0.2 × 0.2 × 0.2 mmWavelength: Mo K0 radiation (0.71073 Å)%: 36.41 cm−1Diffractometer, scan mode: STOE-IPDS II, 22"max: 52°N(hkl)measured, N(hkl)unique: 40712, 3023Criterion for Iobs, N(hkl)gt: Iobs > 2 !(Iobs), 2462N(param)refined: 169Programs: SHELXS-97 [5], SHELXL-97 [6]Table 1. Data collection and handling.H(4A) 8d 0.50 0.5123 0.3039 0.0240 0.059H(4B) 8d 0.50 0.5500 0.2531 −0.0809 0.059H(4C) 8d 0.50 0.5143 0.1930 0.0183 0.059H(5A) 8d 0.3565 0.1402 −0.2244 0.062H(5B) 8d 0.4148 0.0884 −0.1405 0.062H(5C) 8d 0.4506 0.1487 −0.2394 0.062H(6A) 4c 0.2050 ¼ −0.3509 0.065H(6B) 8d 0.50 0.2764 0.1945 −0.2942 0.065H(6C) 8d 0.50 0.2764 0.3055 −0.2942 0.065H(7A) 8d 0.0950 0.1422 −0.2300 0.064H(7B) 8d 0.0892 0.1408 −0.0985 0.064H(7C) 8d 0.1602 0.0878 −0.1592 0.064H(13A) 8d 0.2232 −0.0230 0.1579 0.049H(13B) 8d 0.2358 0.0556 0.0666 0.049H(13C) 8d 0.1792 0.0748 0.1700 0.049H(14A) 8d 0.2180 0.0602 0.4315 0.071H(14B) 8d 0.1774 0.1302 0.3461 0.071H(14C) 8d 0.2313 0.1696 0.4441 0.071H(15A) 8d 0.4155 0.0798 0.4963 0.078H(15B) 8d 0.3652 0.1731 0.5113 0.078H(15C) 8d 0.4546 0.1779 0.4672 0.078H(16A) 8d 0.5337 0.0563 0.2830 0.066H(16B) 8d 0.5340 0.1652 0.3082 0.066H(16C) 8d 0.5346 0.1292 0.1836 0.066H(17A) 8d 0.4163 −0.0256 0.0795 0.052H(17B) 8d 0.4513 0.0720 0.0393 0.052H(17C) 8d 0.3617 0.0443 0.0105 0.052Table 2. Atomic coordinates and displacement parameters (in Å2).Atom Site Occ. x y z Uiso_____________* Correspondence author (e-mail: anke.spannenberg@catalysis.de)94 Hf(C10H15)2(Me3SiC2SiMe3CO2)C(1) 4c 0.3254(3) ¼ 0.0119(3) 0.021(2) 0.012(2) 0.020(2) 0 0.003(2) 0C(2) 4c 0.2471(2) ¼ −0.0194(3) 0.022(2) 0.016(2) 0.018(2) 0 0.000(2) 0C(3) 4c 0.1864(2) ¼ 0.0726(4) 0.021(2) 0.019(2) 0.024(2) 0 −0.002(2) 0C(4) 4c 0.5082(3) ¼ −0.0249(4) 0.025(2) 0.049(3) 0.043(3) 0 0.000(2) 0C(5) 8d 0.4074(2) 0.1441(3) −0.1856(3) 0.045(2) 0.051(2) 0.028(2) 0.012(2) 0.004(2) −0.010(2)C(6) 4c 0.2430(3) ¼ −0.2898(4) 0.046(3) 0.063(3) 0.021(2) 0 −0.001(3) 0C(7) 8d 0.1256(2) 0.1424(3) −0.1614(3) 0.045(2) 0.043(2) 0.039(2) −0.011(2) −0.005(2) −0.009(2)C(8) 8d 0.2972(2) 0.0809(2) 0.2086(3) 0.024(1) 0.014(1) 0.029(2) −0.003(1) −0.003(2) 0.006(1)C(9) 8d 0.2967(2) 0.1127(2) 0.3185(3) 0.034(2) 0.024(2) 0.025(2) −0.001(1) 0.003(1) 0.009(1)C(10) 8d 0.3759(2) 0.1332(2) 0.3497(3) 0.042(2) 0.021(2) 0.026(2) 0.003(2) −0.009(2) 0.004(1)C(11) 8d 0.4251(2) 0.1176(2) 0.2569(3) 0.023(2) 0.020(1) 0.039(2) 0.004(1) −0.009(1) 0.001(1)C(12) 8d 0.3765(2) 0.0837(2) 0.1703(3) 0.021(2) 0.016(1) 0.029(2) 0.001(1) −0.001(1) 0.001(1)C(13) 8d 0.2279(2) 0.0439(2) 0.1453(3) 0.029(2) 0.022(2) 0.046(2) −0.007(1) −0.006(2) 0.002(2)C(14) 8d 0.2245(2) 0.1187(3) 0.3914(3) 0.054(2) 0.048(2) 0.039(2) −0.006(2) 0.023(2) 0.012(2)C(15) 8d 0.4054(3) 0.1418(3) 0.4663(3) 0.082(3) 0.041(2) 0.034(2) 0.001(2) −0.024(2) 0.007(2)C(16) 8d 0.5147(2) 0.1170(3) 0.2580(4) 0.024(2) 0.038(2) 0.069(3) 0.008(2) −0.016(2) −0.006(2)C(17) 8d 0.4038(2) 0.0399(2) 0.0660(3) 0.036(2) 0.023(2) 0.045(2) 0.001(1) 0.008(2) −0.010(2)Hf(1) 4c 0.33360(1) ¼ 0.20230(1) 0.01624(8) 0.01529(8) 0.01617(8) 0 0.00059(9) 0O(1) 4c 0.2143(2) ¼ 0.1743(2) 0.015(1) 0.027(2) 0.020(2) 0 −0.000(1) 0O(2) 4c 0.1151(2) ¼ 0.0541(3) 0.019(2) 0.044(2) 0.029(2) 0 −0.001(1) 0Si(1) 4c 0.40801(7) ¼ −0.0942(1) 0.0217(6) 0.0314(7) 0.0219(6) 0 0.0063(5) 0Si(2) 4c 0.18724(7) ¼ −0.1545(1) 0.0252(7) 0.0279(6) 0.0196(5) 0 −0.0035(5) 0Table 3. Atomic coordinates and displacement parameters (in Å2).Atom Site x y z U11 U22 U33 U12 U13 U23Acknowledgments. This work was supported by the Deutsche Forschungs-gemeinschaft (GRK 1213) and the Russian Foundation for Basic Research(Project code 09-03-00503). Funding and facilities provided by the Leibniz-Institut für Katalyse e. V. an der Universität Rostock are gratefully acknowl-edged.References1. Beweries, T.; Burlakov, V. V.; Bach, M. A.; Arndt, P.; Baumann, W.;Spannenberg, A.; Rosenthal, U.: Complexation of Bis(trimethylsilyl)-acetylene by Decamethylhafnocene To Give the HafnacyclopropeneCp*2Hf(+2-Me3SiC2SiMe3): An Unusually Strong Metal-Alkyne Interac-tion. Organometallics 26 (2007) 247-249.2. Beweries, T.; Burlakov, V. V.; Peitz, S.; Arndt, P.; Baumann, W.;Spannenberg, A.; Rosenthal, U.: Synthesis and Reactions of Cp*2Hf(+2-PhC2SiMe3) with Water and Carbon Dioxide. Organometallics 27 (2008)3954-3959.3. Pellny, P.-M.; Burlakov, V. V.; Baumann, W.; Spannenberg, A.;Rosenthal, U.: The Influence of the Ligands Cp*(+5-C5Me5) and Cp(+5-C5H5) on the Stability and Reactivity of Titanocene and ZirconoceneComplexes: Reactions of the Bis(trimethylsilyl)acetylene Permethyl-metallocene Complexes (+5-C5Me5)2M(+5-Me3SiC2SiMe3), M = Ti, Zr,with H2O and CO2. Z. Anorg. Allg. Chem. 625 (1999) 910-918.4. Beweries, T.: Beiträge zu gewöhnlichen und ungewöhnlichen Fünfring-Metallacyclen der 4. Nebengruppe. Master Thesis, University of Rostock2006.5. Sheldrick, G. M.: SHELXS-97. Program for the Solution of Crystal Struc-tures. University of Göttingen, Germany 1997.6. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of CrystalStructures. University of Göttingen, Germany 1997.

Crystal structure of 1, 1-bis(pentamethylcyclopentadienyl)-4, 5-bis(trimethyIsilyl)-1-hafnafuran-3-one, Hf(C10H15) 2(Me3SiC2SiMe3CO2)

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Crystal structure of 1, 1-bis(pentamethylcyclopentadienyl)-4, 5-bis(trimethyIsilyl)-1-hafnafuran-3-one, Hf(C10H15) 2(Me3SiC2SiMe3CO2)

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