Bis(1,2,3,4‐η⁴‐anthracene)ferrate(1−): A Paramagnetic Homoleptic Polyarene Transition‐Metal Anion

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

“…The relative intensities of the signals as well as their angular variations clearly indicate that they are due to a molybdenum centred radical species ( 95 Mo: I ¼ 5/2, g n ¼ À0.3656, natural abundance: 15.9%, 97 Mo: I ¼ 5/2, g n ¼ À0.3734, natural abundance: 9.6%). An additional coupling with a spin 1 2 nucleus, attributed to 31 P, is also observed. The intensity of these signals irreversibly decreases when temperature increases; these lines are no more detected above 180 K.…”

“…Transition metal complexes with a 17-electron configuration continue to present considerable interest in both fundamental and applied chemistry [1][2][3][4]. These species are invoked as intermediates in many syntheses; some of them, for example, have been proposed as catalysts for olefin metathetical polymerization [5], while metal-centred radicals derived from carbonyl complexes, are frequently used for their exceptional substitutional lability [6][7][8].…”

Structurally Distinct Homoleptic Anthracene Complexes, [M(C14H10)3]2−, M=Titanium, Zirconium, Hafnium: Tris(arene) Complexes for a Triad of Transition Metals

“…However, crystal structures of the [K( [18] [11,30] Facile chemical reactions of naphthalenehafnate 6 with CO and anthracene, mentioned above, are consistent with its characterization as a source of the to date unknown atomic Hf 2À . Because of the paucity of well-defined anionic homoleptic 1,3,5,7-cyclooctatetraene (cot) transition metal complexes, of which only [M(h-cot) 3 ] À (M = Nb, Ta) [31] and [Co(hcot) 2 …”

“…[2,8] We report herein the synthesis, isolation, and structural characterization of the first set of homoleptic polyarenemetalates for a triad of transition metals: the tris(anthracene)metalates(2À), [M-(C 14 H 10 ) 3 ] 2À , M = Ti (2), Zr (3), and Hf (4). In addition, the triad of Group 4 elements has been "completed" for homoleptic naphthalene complexes with access to the tris(naphthalene)metalates(2À), [M(C 10 H 8 ) 3 ] 2À , for M = Ti (5), Hf (6). Hafnates 4 and 6 are of particular interest as they are the first polyarene complexes of Hf and are unprecedented examples of hydrocarbon-stabilized negative-valent hafnium, Hf 2À , previously established for only one other compound, [Hf(CO) 6 ] 2À .…”

“…[3] The first well-characterized homoleptic polyarenemetalate, tris(naphthalene)zirconate(2À) (1), [4] was reported nearly 15 years ago, and related complexes are now documented for Nb, [5] Ta, [6] Fe, [3] and Co. [7] However, little or nothing is known about the analogous metalates of other d-block elements. [2,8] We report herein the synthesis, isolation, and structural characterization of the first set of homoleptic polyarenemetalates for a triad of transition metals: the tris(anthracene)metalates(2À), [M-(C 14 H 10 ) 3 ] 2À , M = Ti (2), Zr (3), and Hf (4). In addition, the triad of Group 4 elements has been "completed" for homoleptic naphthalene complexes with access to the tris(naphthalene)metalates(2À), [M(C 10 H 8 ) 3 ] 2À , for M = Ti (5), Hf (6).…”