{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,17]],"date-time":"2025-10-17T13:20:17Z","timestamp":1760707217457},"reference-count":22,"publisher":"Wiley","issue":"2","license":[{"start":{"date-parts":[[2003,12,22]],"date-time":"2003-12-22T00:00:00Z","timestamp":1072051200000},"content-version":"vor","delay-in-days":4707,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew. Chem. Int. Ed. Engl."],"published-print":{"date-parts":[[1991,2]]},"DOI":"10.1002\/anie.199101851","type":"journal-article","created":{"date-parts":[[2003,12,31]],"date-time":"2003-12-31T00:13:04Z","timestamp":1072829584000},"page":"185-187","source":"Crossref","is-referenced-by-count":52,"title":["Alkyl\u2010 and Arylrhenium Trioxides"],"prefix":"10.1002","volume":"30","author":[{"given":"Wolfgang A.","family":"Herrmann","sequence":"first","affiliation":[]},{"given":"Carlos C.","family":"Romao","sequence":"additional","affiliation":[]},{"given":"Richard W.","family":"Fischer","sequence":"additional","affiliation":[]},{"given":"Paul","family":"Kiprof","sequence":"additional","affiliation":[]},{"given":"Claude","family":"de M\u00e9ric de Bellefon","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2003,12,22]]},"reference":[{"key":"e_1_2_1_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr60300a003"},{"key":"e_1_2_1_1_3","doi-asserted-by":"publisher","DOI":"10.1021\/cr60300a004"},{"key":"e_1_2_1_1_4","first-page":"286","volume-title":"Organotransition Metal Chemistry","author":"Yamamoto A.","year":"1986"},{"key":"e_1_2_1_2_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac197230030575"},{"key":"e_1_2_1_2_3","first-page":"802","volume":"1982","author":"Dawoodi Z.","journal-title":"J. Chem. Soc. Chem. Commun."},{"key":"e_1_2_1_2_4","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(00)91205-2"},{"key":"e_1_2_1_2_5","doi-asserted-by":"publisher","DOI":"10.1021\/ja00328a059"},{"key":"e_1_2_1_3_2","unstructured":"(a) Examples: [Cr(C2H5)4] (unstable unknown) [Cr(t\u2010C4H9)4](stable;"},{"key":"e_1_2_1_3_3","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)81814-8"},{"key":"e_1_2_1_3_4","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)86552-3"},{"key":"e_1_2_1_3_5","unstructured":"(b) [Ti(CH3)4] (unstable) [Ti(CH3)4(bpy)] (stable) [Ti(l\u2010norbornyl)4] (stable)."},{"key":"e_1_2_1_4_2","unstructured":"In the series of organometallic oxides of the type R2MOb stable ethyl complexes (R = C2H5) are unknown. Thus [(CH3)4OsO] is a stable compound in the gas phase whereas [(C2H5)4OsO] decomposes above \u221260 \u00b0C ton\u2010butane ethane ethylene and reduced osmium oxides:W. A.Herrmann S. J.Eder P.Kiprof K.Rypdal P.Watzlowik unpublished results 1990."},{"key":"e_1_2_1_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19881000322"},{"key":"e_1_2_1_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198803941"},{"key":"e_1_2_1_5_4","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(89)87229-8"},{"key":"e_1_2_1_6_2","unstructured":"Experimental Procedure:A solution of sublimed Re2O7(489 mg 1 mmol) in 15 mL of THF (< 1 ppm H2O) was treated at dry\u2010ice temperature with exactly 0.5 mmol of ZnR2(1 M solution in THF). The colorless stirred solution was warmed to \u22125\u00b0C (R = C2H5) \u221230\u00b0C (R =i\u2010C4H9) or 20\u00b0C(R = CH2Si(CH3)3 C6H5). The THF was evaporated in vacuo and the residue was extracted with cold (!)n\u2010pentane. The yellow extract was filtered through a cannula and concentrated to about 10 mL at \u221230 \u00b0C under vacuum. Cooling the solution to dry\u2010ice temperature afforded colorless crystals which were dried under high vacuum at \u221230 \u00b0C. Yield 60\u201370%. Gas chromatogram (HP A\u20105890): fused silica HP\u20101 50 m 200 kPa He 120\/180\u00b0C 20\u00b0C\/min 180\/200\u00b0C 40\u00b0C\/min:tR= 7.23 min. 2a: Colorless crystals fromn\u2010pentane m.p. \u221221 \u00b0C. IR (CS2): \u1e7d [cm\u22121] = 996 (m) 961 (vs) 950 (s) 927 (m). IR (gas phase): \u1e7d [cm\u22121] = 970 (vs).1H NMR (400 MHz): \u03b4 = 2.19 (t. 3H; CH3) 3.66 (q 2H; CH2) (CD2Cl2 \u221220\u00b0C); \u03b4 = 1.29 (t 3H; CH3) 2.31 (q 2H; CH2) (C6D6 20\u00b0C). (13C1H} NMR (100.5 MHz C6D6 20 \u00b0C): \u03b4 = 18.20(CH3) 36.56 (CH2). EI\u2010MS (70eV):m\/z264 (M\u2295 rel int. 1 %) 236 ([M\u2212 C2H4]\u2295 100%) correct isotopic pattern.2b: Colorless crystals fromn\u2010pentane (\u221280 \u00b0C) colorless liquid at room temperature. IR (CS2): \u1e7d [cm\u22121] = 994 (w\u2010m) 962 (vs).1HNMR (400MHz C6D6 20\u00b0C): \u03b4 = 0.54 (d 6H 2J(H H) = 6.7 Hz; CH3) 2.42 (d 2H 2J(H H) = 6.1 Hz; CH2) 1.91 (tq 1H; CH);13C{1H}NMR (100.5 MHz C6D6 20\u00b0C): \u03b4 = 24.08 (CH3) 31.48 (CH2) 52.15 (CH); El MS (70 eV):m\/z292 (M\u2295 rel. int. 1 %) 291 ({M\u2212 H]\u00b0 ca. 30%) 277 ([M\u2212 CH3]\u2295 100%).2c: Colorless crystals fromn\u2010pentane m.p. 30 \u00b0C slow dec. at room temperature; the crystals turn black in water. IR (CS2): \u1e7d [cm\u22121] = 990 (s) 965 (vs) 957 (vs) 925 (m);1HNMR (400 MHz C6D6 20\u00b0C): \u03b4 = \u22120.16 (s 9H; CH3) 1.60 (s 2H; CH2).13CNMR (100.5MHz C6D6 20\u00b0C): \u03b4 = \u22120.74 (q 1J(C H) = 120 Hz; CH3) 34.35 (t 1J(C H) = 125 Hz CH2).17ONMR (54.2 MHz n\u2010pentane 20\u00b0C): \u03b4 = 808 (standard; ext. H2O \u03b4 = 0); for comparison: \u03b4 = 835 for CH3ReO3inn\u2010pentane. El MS (70 eV):m\/z322 (M\u2295 rel. int. 1%) 307 ([M \u2212 CH3]\u2295 100%).2d: Colorless crystalline powder fromn\u2010pentane m.p. = 45 \u00b0C. IR (KBr): \u1e7d [cm\u22121] = 986 (m) 956 (vs);1HNMR (400 MHz CD2Cl2 20\u00b0C): \u03b4 = 7.87 (d 2H 3J(H H) = 7.9 Hz;o\u2010C6H5) 7.69 (t 1 H 3J(H H) = 7.3 Hz;p\u2010C6H5) 7.63 (t 2H;m\u2010C6H5).13C{1H} NMR (100.5 MHz CD2C12 20\u00b0C): \u03b4 = 155.5 (ReC) 142.5 (o\u2010C6H5) 135.5 (p\u2010C6H5) 130.4 (m\u2010C6H5). El MS (70 eV):m\/z312 (M\u2295 rel. int. 4%) 154 (C12H10 100%)."},{"key":"e_1_2_1_7_2","unstructured":"2a. quinuclidine orange air\u2010stable crystals m.p. = 109 \u00b0C (dec.). IR (KBr): \u1e7d [cm\u22121): 922 (vs).2c. quinuclidine: lemon\u2010yellow crystals m.p. 135\u00b0C.1HNMR(400 MHz C6D6 20\u00b0C): \u03b4 = 0.15(s 9H;CH3) 1.48 (s 2H; ReCH ) 0.90\/2.25 (2 m 2 \u00d7 6H; CCH2) 1.17 (m 1 H; CH).13C{1H} NMR (100.5 MHz. C6D6 20\u00b0C): \u03b4 = \u22120.16 (SiCH3) 35.81 (SiCH2) 20.81 (CH) 25.76\/47.41 (CCH2); IR: \u1e7d [cm\u22121] = 926 (vs) (CS2) 922 (vs) (KBr); FD MS (n\u2010pentane):m\/z433 (M\u2295)."},{"key":"e_1_2_1_8_2","unstructured":"2a\u2010 quinuclidine: Orange columns from CS2solution (\u221225\u00b0C). 0.51 \u00d7 0.15 \u00d7 0.10 mm; systematic absences:h01(h + I = 2n+ 1);0k0(k = 2n+ 1); space group: monoclinic P21\/n(Int. Tab. No. 14);a= 664.3(3) b= 881.1(4) c= 2009.1(9)pm \u03b2 = 98.98(2)\u00b0 V= 1161 \u00d7 106 pm3;Z= 4;F000= 712; \u03f1calcd= 2.141 g cm\u22123; Enraf\u2010Nonius CAD\u20104. MoK\u03b1(\u03bb = 71.073 pm) graphite monochromator;T= 23 \u00b1 3\u00b0 C; measuring range 2.0 < \u03b8 < 25.0\u00b0; \u03c9 scan; 1900 unique reflections withI> 0.0 used for refinement;R= 0.034;Rw= 0.018; GOF = 1.889. Direct methods difference Fourier technique; empirical absorption correction \u03bc = 105.9 cm\u22121 nine reflections; decomposition \u221211.2% in 34 h. anisotropic correction. Hydrogen atom positions were calculated (d(C\u2010H) = 95 pm) and included in the structure factor calculation. but not refined. Anomalous dispersion was taken into consideration. Shift\/error: < 0.01 in the last cycle of the refinement; residual electron density: + 0.90 eO\u00c5\u22123at 75 pm and \u22121.07 eoA\u22123at 74 pm from the rhenium atom.2c. quinuclidine: Yellow cubes fromn\u2010pentane (25 \u00b0C); 0.56 \u00d7 0.30 \u00d7 0.21 mm; systematic absences:h0l(l = 2n+ 1);0k0(k = 2n+ 1): space group monoclinic.P21\/c(Int. Tab. No. 14);a= 667.7 (3).b= 2065.8(4) c= 1140.9(7) pm \u03b2 = 96.42(2)\u00b0 V= 1564 \u00d7 106pm3;Z= 4;F000= 840; \u03f1calcd= 1.837 g cm\u22123; Enraf\u2010Nonius CAD\u20104. MoK\u03b1. (\u03bb = 71.073 pm) graphite monochromator; T = 23 \u00b1 3\u00b0C; measuring range: 2.0 < \u03b8 < 25.0\u00b0; 2429 unique reflections (I> 0.0);R= 0.039;Rw= 0.021; GOF = 1.848. Patterson methods difference Fourier technique; empirical absorption correction \u03bc = 79.5 cm\u22121 eight reflections; 23.1 % decomposition corrected. Hydrogen atom positions were calculated (d(C\u2010H) = 95 pm) and included in the structure factor calculation but not refined. Anomalous dispersion was taken into consideration. Shift\/error: < 0.01 in the last cycle of the refinement; residual electron density: + 0.64 eo\u00c5\u22123at 100 pm and \u22120.80 eo\u00c5\u22123at 90 pm from the rhenium atom."},{"key":"e_1_2_1_9_2","unstructured":"W. A.Herrmann C. C.Romao P.Kiprof J.Behm M. R.Cook M.Taillefer J Organomet. Chem. in press."},{"key":"e_1_2_1_10_2","unstructured":"W. A.Herrmann S. J.Eder unpublished results 1990."},{"key":"e_1_2_1_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(90)85211-G"},{"key":"e_1_2_1_12_2","unstructured":"Note added in proof (Jan. 15 1991): Further studies have shown that radical\u2010type degradation pathways (e.g. Re\uf8ffC bond cleavage) are of importance and are connected with the stability of the radicals R; for example.2feliminates butene and isobutane [Eq. (b)] but also large amounts of 2 2 3 3\u2010tetramethylbutane. The system Re2O7\/Zn(CH2C6H5)2 yields a little toluene and much bibenzyl at \u221280\u00b0 C (compare decomposition of2d). Cyclopentadienylrhenium trioxide. [(C5H5)ReO3] is stable under ordinary conditions representing the first C5H5complex of a metal in an oxidation state greater than 5 (W. A.Herrmann M.Taillefer C.de M\u00e9ric de Bellefon unpublished results 1990)."}],"container-title":["Angewandte Chemie International Edition in English"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.199101851","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.199101851","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,10,23]],"date-time":"2023-10-23T05:08:12Z","timestamp":1698037692000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.199101851"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[1991,2]]},"references-count":22,"journal-issue":{"issue":"2","published-print":{"date-parts":[[1991,2]]}},"alternative-id":["10.1002\/anie.199101851"],"URL":"https:\/\/doi.org\/10.1002\/anie.199101851","archive":["Portico"],"relation":{},"ISSN":["0570-0833"],"issn-type":[{"value":"0570-0833","type":"print"}],"subject":[],"published":{"date-parts":[[1991,2]]}}}