Sulfur Compounds, 199. Novel Titanocene Thiolato Complexes and Their Application in Preparing New Sulfur‐Containing Heterocycles

Abstract

Treatment of Cp2Ti(CO)2 (3) with the di‐ and polysulfanes 1,2,4‐(CH2)2S3, C4S6 (9), C,7H10S3 (11), 1,2,4,6‐(CH2)3S4 (16), C6H10S6(19), and S6 affords the titanocene chelate complexes Cp2TiS3(CH2)2 (8), (Cp2Ti)2C4S6 (10), Cp2TiS3C7H10 (13), Cp2TiS2C7H10 (14), Cp2TiS4(CH2)3 (17), Cp,2TiS6C6H6H10 (20), and Cp2TiS8 (23). 14 is also obtained from Cp2TiCl2 (1) and the geminal dithiol of norbornene. The analogous reaction with the dithiol of dicyclopentadiene yields Cp2TiS2C10H12 (15). In ligand transfer reactions, 8 reacts with SCl2 to give 1,2,3,5‐tetrathiane (25), 10 provides 9 on reaction with Cl2, 13 when treated with S2Cl2 affords C7H10S5 (12), 15 reacts with S2Cl2Cl2 to give C10H12S4. 17 and SCl2 yield 1,2,3,5,7‐pentathiepane (18), 20 is converted to C6H10S7 (22) on reaction with SCl2, and 23 yields S10 and 1,2,‐C6H4(SCl)2, respectively. With phosgene, thiophosgene, and thionyl chloride, compound 15 yields the corresponding dithiocarbonate 26, the trithiocarbonate 27 and the trisulfane 2‐oxide 28. The structure of 27 was determined by X‐ray crystallography.

Novel Nine-Membered Titanaheterocycles – Structure, ab initio Calculations, and Preparative Use towards the Selective Synthesis of Substituted Cyclopentanols

“…4a) readily react under mild, non-basic conditions with titanacycles are known as well, but most of them lack car-dicarbonyltitanocenes 3 [18] to furnish the corresponding bon in their metallacycle, as for instance TiS 8 systems. [4] [13] nine-membered bis-unsaturated metallacycles 5 right away We reported [14] on the synthesis of "carbon-rich" bis(η 5 -without five-membered species of type 1 being detectable cyclopentadienyl)titanadioxacyclononadienes 5 by a novel intermediates [14] . Oxidative addition of two ketone units, coupling of two α,β-unsaturated ketones with Cp 2 Ti(CO) 2 , loss of two equivalents of CO and exclusive trans-β,β coupand recently Okuda [15] published the X-ray structures of ling are the features of this reaction, which at first seemed nine-membered titanacycles built up from a 2,2Ј-ethylene-to be restricted to bis(aryl)-substituted ketones, though.…”

“…propanes, [3] titanaheterocyclopentanes and -pentenes, [4] [5] [6] [7] [8] [9] [10] [11] or titana-2,7-dioxacyclohepta-3,5-We have recently shown that α,β-unsaturated arylketones dienes. [6] [11] [12] Structurally characterized nine-membered (e.g.…”

“…Whereas most of the publications focussed on systems featuring four- [1] , six- [2] [3] [4] , eight- [4] [5] or ten-mem-Results and Discussion bered [5] rings, we were interested in the chemistry of the Synthesis of "Symmetric" Titana-2,9-dioxacyclonona-3,7-dienes 5;…”

“…Ϫ 13 C NMR (100.4 MHz, C 6 D 6 ): δ ϭ 45.1 (C-5, C-6), 92.1, 92.7 (CHϭCHPh), 1 h), the solution was filtered at ambient temperature, 5 ml of hexane was added and the resulting precipitate was collected on a sin-102.2 (C-4, C-7), 116. 2 (Cp),126.4,126.7,127.9,128.6,129.7,130.1 (CH ar ),145.2, 3.12 (s,3 H,CH 3 ),4.16 (dd,3 J ϭ 5.62,5.86 (5,1 H,4.70 (d,3 J ϭ 5.62 Hz,1 H,5.33 (d,[3][4][5]1 H,5.67 (s,5 H,Cp),5.70 (s,5 H,Cp),5.80 (d,3 J ϭ 3, 4.46 (dd,3 J ϭ 5.62,123.1 (CHϭCHPh),125.8,126.3,127.1,127.9,132.8,134.5,135.3,5.86 Hz,1 H, 1,129.7,130.1,130.7,130.9,134.1,135.7,137.2,(5,138.9 (CH ar ),141.2,143.8,144.3,, 159.1 oxyphenyl)...…”

“…133.7,134.5,136.1,137.8,138.2 (CH ar ), 142. 2,142.9,144.1,158.5,159.6,160.6 (COCH 3 ),162.2, , 1610, 1450, 1250 : δ ϭ 3.42 (s, dienyl) -5-phenyl-6-β-(trans-phenylethenyl)-1-titana-2,9- 4,126.7,127.3,127.7,129.5,132.7,134.7,135.5,136.5,137.5,138.1,138.9 (CH ar ), 142. 2,142.5,144.4,156.5,156.9 (5,5,163.1,.…”